Compositions, urethane prepolymers, and related methods and uses

Abstract

The composition includes (A) a carbinol-functional siloxane and (B) a polyisocyanate. The carbinol-functional siloxane (A) is not prepared by a hydrosilylation reaction. Further, the composition contains less than 5 mole % of (C) a compound of formula RO a -(C b H 2b O) c -R 1 wherein R is an ethylenically unsaturated group and R 1 is H or a hydrocarbyl group, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 at each moiety designated by subscript c, subscript c is 0 to 500, with the proviso that subscripts a and c are not simultaneously 0. Also disclosed is a urethane prepolymer comprising the reaction product of the composition.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and all benefits of U.S. Provisional Patent Application No. 63 / 330,517, filed April 13, 2022, the contents of which are incorporated herein by reference.

[0002] The present disclosure relates generally to compositions, and more specifically to compositions for preparing urethane prepolymers, associated processes, and end uses thereof. [Background technology]

[0003] Carbinol-functional siloxanes are known in the art and are utilized in a variety of end-use applications, including curable compositions such as sealants, adhesives, and the like. Conventional carbinol-functional siloxanes are prepared by hydrosilylation reactions in which an organopolysiloxane having silicon-bonded hydrogen atoms is hydrosilylated with an alcohol or polyether having one terminal unsaturated group in the presence of a hydrosilylation catalyst. A molar excess of the alcohol and / or polyether is generally utilized to ensure that no residual silicon-bonded hydrogen atoms remain, and to allow for isomerization of the terminal unsaturated groups of the alcohol or polyether, which reduces the reactivity of the hydrosilylation. As a result, conventional carbinol-functional siloxanes are generally utilized as reaction products that contain both the conventional carbinol-functional siloxane as well as residual amounts of the alcohol and / or polyether (or their isomerized forms), which may often constitute about 30 mol% of the reaction product. In other words, residual alcohol and / or polyether are inherently present with the conventional carbinol-functional siloxane prepared by hydrosilylation.Because the boiling point temperatures of the conventional carbinol-functional siloxane and such alcohol or polyether are similar, it is difficult and impractical to purify the conventional carbinol-functional siloxane by removing residual amounts of alcohol and / or polyether from the reaction product, for example, by distillation or stripping, especially when the conventional carbinol-functional siloxane is linear and has a low degree of polymerization.The residual amount of alcohol and / or polyether causes undesirable by-products and side reactions when the conventional carbinol-functional siloxane is used, for example, in further reactions.The presence of residual amounts of alcohol and / or polyether can have serious and undesirable effects, especially with respect to the preparation of prepolymers using the conventional carbinol-functional siloxane. Summary of the Invention

[0004] Disclosed is a composition comprising (A) a carbinol-functional siloxane and (B) a polyisocyanate. The carbinol-functional siloxane (A) is not prepared by a hydrosilylation reaction. Further, the composition contains less than 5 mole % of (C) a compound of formula RO a -(C b H 2b O) c -R 1 wherein R is an ethylenically unsaturated group and R 1 is H or a hydrocarbyl group, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 at each moiety designated by subscript c, subscript c is 0 to 500, with the proviso that subscripts a and c are not simultaneously 0.

[0005] Also disclosed is a urethane prepolymer, including a reaction product of the composition. Also disclosed is a cured product of the composition and the urethane prepolymer, respectively.

[0006] Also disclosed is a method of preparing the composition, the method comprising combining (A) a carbinol-functional siloxane and (B) a polyisocyanate. [Brief description of the drawings]

[0007] Various advantages and aspects of the present disclosure may be understood by consideration of the following detailed description when considered in conjunction with the accompanying drawings. [Figure 1] 1 shows RI signal as a function of elution time for example polyether-functional siloxane compositions of the present disclosure and comparative polyether-functional siloxane compositions. [Diagram 2] 1 shows the RI signal as a function of elution time for the isocyanate-functional prepolymers of Example 1 and Comparative Example 1, respectively. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Compositions are disclosed that are particularly suitable for preparing urethane prepolymers, and urethane prepolymers are also disclosed, along with methods for their preparation and use.

[0009] The composition comprises (A) a carbinol-functional siloxane and (B) a polyisocyanate. In certain embodiments, (A) the carbinol-functional siloxane comprises an average of at least two carbinol functional groups per molecule. In these embodiments, the carbinol functional groups can be the same or different from each other. The carbinol functional groups on the organopolysiloxane are distinct from silanol groups, the carbinol functional groups comprising carbon-bonded hydroxyl groups and the silanol functional groups comprising silicon-bonded hydroxyl groups. In other words, the carbinol functional groups are of the formula -COH, whereas the silanol functional groups are of the formula -SiOH. These functional groups function differently, for example, the silanol functional groups can easily condense to provide siloxane (-Si-O-Si-) bonds, which generally does not occur with the carbinol functional groups (at least under the same catalysis as the hydrolysis of the silanol functional groups).

[0010] In certain embodiments, the carbinol functional groups are independently represented by the general formula -DO a -(C b H 2b O) c -H, where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 at each moiety designated by subscript c, and subscript c is 0 to 500, with the proviso that subscripts a and c are not simultaneously 0.

[0011] In one embodiment, the subscript c is at least 1, such that at least one of the carbinol functional groups has the general formula: -DO a -[C2H4O] x [C3H6O] y [C4H8O] z -H where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, and the subscript a is 0 or 1, with 0≦x≦500, 0≦y≦500, and 0≦z≦500, with the proviso that 1≦x+y+z≦500. In these embodiments, the carbinol functionality may alternatively be referred to as a polyether group or moiety, but the polyether group or moiety has the formula -COR 0 Instead of -COH, R 0 is a monovalent hydrocarbon radical. As understood in the art, the moieties designated by subscript x are ethylene oxide (EO) units, the moieties designated by subscript y are propylene oxide (PO) units, and the moieties designated by subscript z are butylene oxide (BO) units. The EO, PO, and BO units, if present, can be in block or randomized form in the polyether group or moiety. The relative amounts of EO, PO, and BO units, if present, can be selectively controlled based on the desired properties of the (A) carbinol-functional siloxane, the composition, and the resulting polyurethane article. For example, the molar ratio of such alkylene oxide units can affect hydrophilicity and other properties.

[0012] In another embodiment, subscript c is 0 and subscript a is 1, such that at least one of the carbinol functional groups has the general formula: -D-OH, where D is described above. In these embodiments, the carbinol functional group having this general formula is not a polyether group or moiety.

[0013] Regardless of the independent selection of the carbinol functionality of component (A), component (A) is typically substantially linear. By substantially linear, it is meant that component (A) comprises, consists essentially of, or consists only of M and D siloxy units. As is readily understood in the art, M siloxy units are those having the formula [R 2 3SiO 1 / 2], and the D siloxy units are of the formula [R 2 2SiO 2 / 2 Conventionally, the M and D siloxy nomenclature has been utilized in conjunction with methyl substitution only. However, for purposes of this disclosure, in the above M and D siloxy units, each R 2 are independently selected from a substituted or unsubstituted hydrocarbyl group or a carbinol functional group, provided that at least one R 2 is a carbinol functional group. When the M siloxy unit contains at least one carbinol functional group, the carbinol functional group is terminal. When the D siloxy unit contains at least one carbinol functional group, the carbinol functional group is pendant. The substantially linear organopolysiloxane has an average formula: 2 a’ SiO (4-a’) / 2 (In the formula, each R 2 are independently selected and defined above, provided that at least one R 2 is a carbinol functional group, and the subscript a' is selected such that 1.9≦a'≦2.2.

[0014] In general, R 2Suitable hydrocarbyl groups for may be independently linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be independently monocyclic or polycyclic. Linear and branched hydrocarbyl groups may be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, variants, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycyloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon or substituted hydrocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above in which one or more hydrogen atoms have been replaced with a halogen atom, such as F or Cl.Specific examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of halogenated aryl groups include the above-mentioned aryl groups, in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0015] In specific embodiments, each R that is not a carbinol functional group 2 are independently selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, or alternatively 1 carbon atom.

[0016] In other embodiments, (A) the carbinol functional siloxane may contain at least some branching due to the presence of T or Q siloxy units. As is understood in the art, T units are represented by the formula [R 2 SiO 3 / 2 Q siloxy units are of the formula [SiO 4 / 2 wherein R 2is defined above. However, (A) carbinol-functional siloxane typically does not contain such T and Q siloxy units. By "at least some" it is meant that (A) carbinol-functional siloxane may contain up to 5 mol%, alternatively up to 4 mol%, alternatively up to 3 mol%, alternatively up to 2 mol%, alternatively up to 1 mol%, alternatively 0 mol% of T and Q siloxy units based on all siloxy units present in (A) carbinol-functional siloxane. If such branching is present in (A) carbinol-functional siloxane, it is typically due to T siloxy units rather than Q siloxy units. Typically, in view of the desired viscosity, (A) carbinol-functional siloxane is not a gum or resin, but a flowable liquid at room temperature, including in the absence of a solvent or carrier vehicle. The rubber or resin may be a liquid at room temperature when dissolved or dispersed in a solvent or carrier fluid, however, such solvents may be undesirable in certain end use applications because the solvent typically volatilizes or is otherwise removed during the curing process.

[0017] In embodiments where component (A) is linear, component (A) has the general formula:

[0018] [ka] (In the formula, each R 2 are independently selected and defined above, and at least one R 2is a carbinol functional group, with the proviso that the subscript n is from 0 to 100. The subscript n may alternatively be referred to as the degree of polymerization (DP) of component (A). Typically, DP is directly proportional to viscosity, all else being equal (e.g., substitution and branching), i.e., increasing DP increases viscosity. The subscript n may alternatively be from 0 to 95, alternatively from 0 to 90, alternatively from 0 to 85, alternatively from 0 to 80, alternatively from 0 to 75, alternatively from 0 to 70, alternatively from 0 to 65. Alternatively, the subscript n may be from 5 to 70, alternatively from 10 to 65. In one specific embodiment, the subscript n is from 5 to 30, alternatively from 10 to 20, alternatively from 12 to 20. In alternative specific embodiments, the subscript n is from 28 to 32, alternatively from 29 to 31, alternatively from 30. In alternative specific embodiments, subscript n is between 48 and 52, alternatively between 49 and 51, alternatively between 50. In alternative specific embodiments, subscript n is between 58 and 62, alternatively between 59 and 61, alternatively 60.

[0019] In a specific embodiment, each carbinol functional group has the formula -D-OH, and (A) the carbinol functional siloxane has the following general formula:

[0020] [ka] where D and the subscript n are defined above, and each R 2 are independently selected and defined above, provided that when the above formula contains two carbinol functional groups, at least one R 2 In these embodiments, the carbinol functionality is at the terminus of component (A). These carbinol functionalities may be the same or different from one another based on D. This formula may alternatively be represented as [(HOD-)R 2 2SiO 1 / 2 ]2[Si 2 2O 2 / 2 ]n It can be written as:

[0021] In other embodiments, each carbinol functional group has the general formula -DO a -(C b H 2b O) c -H, where D and the subscripts a-c are defined above, and the carbinol functionality is terminal, such that (A) the carbinol-functional siloxane has the general formula:

[0022] [ka] (In the formula, each R 2 are independently selected and defined above, and D and subscripts a-c are defined above. In a specific embodiment, component (A) has the following general formula:

[0023] [ka] (In the formula, each R 2 are independently selected and defined above, the subscript n is 0 to 100, and each subscript m is independently 1 to 100. In this embodiment, n is typically 0 to 80, alternatively 0 to 60, alternatively 0 to 50, alternatively 0 to 40, alternatively 5 to 35, alternatively 5 to 30, alternatively 5 to 25, alternatively 10 to 20, and each m is 1 to 50, alternatively 1 to 40, alternatively 1 to 30, alternatively 2 to 20, alternatively 5 to 10.

[0024] In other embodiments, each carbinol functional group has the general formula -DO a -(C b H 2b O) c -H, where D and subscripts a-c are defined above, and the carbinol functionality is pendant, such that (A) the carbinol-functional siloxane has the general formula:

[0025] [ka] (In the formula, each R 2 are independently selected and defined above, and each subscript Z represents -DO a -(C b H 2b O) c -H, D and the subscripts a-c are as defined above, and the subscripts p and q are each 1 to 99, with the proviso that p+q≦100. In the above general formula, the siloxy units denoted by subscripts q and p can be randomized or in block form. The above general formula can be used to represent the R siloxy units denoted by subscript q without any requirement of a particular order. 2 2SiO 2 / 2 Units and R denoted by subscript p 2 ZSiO 2 / 2 Based on the number of units, it is intended to represent the average unit formula of component (A) in this embodiment. Thus, this general formula can alternatively be expressed as [(R 2 )3SiO 1 / 2 ]2[(R 2 )2SiO 2 / 2 ] q [(R 2 )ZSiO 2 / 2 ] p where the subscripts q and p are defined above. In these embodiments, the carbinol functionality is a polyether group, and the polyether group is pendant in component (A). Each R 2 When is methyl, this embodiment of component (A) is trimethylsiloxy endblocked and includes dimethylsiloxy units (denoted by the subscript q).

[0026] Specific structures of component (A) are exemplified above, but component (A) can include terminal polyether groups as the carbinol functional groups, or pendant carbinol functional groups that are not polyether groups, or any combination of independently selected carbinol functional groups.

[0027] In certain embodiments, component (A) has a capillary viscosity (dynamic viscosity through a glass capillary) at 25° C. of 1 to 1,000 mPa·s, alternatively 1 to 900 mPa·s, alternatively 10 to 700 mPa·s, alternatively 10 to 600 mPa·s. Capillary viscosity may be measured according to Dow Corning Corporate Test Method CTM 0004 of July 20, 1970. CTM 0004 is known in the art and is based on ASTM D445, IP 71. Typically, when component (A) has pendant polyether groups as carbinol functional groups, component (A) has a higher viscosity than when component (A) contains terminal carbinol functional groups that are not polyether groups (as depicted in the exemplary structures above). For example, when component (A) includes pendant polyether groups, the capillary viscosity at 25° C. is typically from 200 to 900, alternatively from 300 to 800, alternatively from 400 to 700, alternatively from 500 to 600 mPa·s. In contrast, when component (A) includes only terminal carbinol functional groups that are not polyether groups, component (A) may have a capillary viscosity at 25° C. of from greater than 0 mPa·s to 250 mPa·s, alternatively from greater than 0 mPa·s to 100 mPa·s, alternatively from greater than 0 mPa·s to 75 mPa·s, alternatively from 10 mPa·s to 75 mPa·s, alternatively from 25 mPa·s to 75 mPa·s.

[0028] In these or other embodiments, component (A) may have an OH equivalent weight from 100 to 2,000, alternatively from 200 to 1,750, alternatively from 300 to 1,500, alternatively from 400 to 1,200 g / mole. Methods for determining OH equivalent weight based on functionality and molecular weight are known in the art.

[0029] In certain embodiments, the composition comprises component (A) in an amount of from greater than 0 to 75 weight percent, alternatively from 10 to 50 weight percent, alternatively from 10 to 40 weight percent, or alternatively from 10 to 30 weight percent, based on the total weight of the composition.

[0030] As introduced above, the composition further comprises (B) a polyisocyanate, which, as is readily understood in the art, has two or more isocyanate functional groups capable of reacting with the carbinol functional groups of (A) the carbinol-functional siloxane.

[0031] Suitable (B) polyisocyanates have two or more isocyanate functional groups, including conventional aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates. (B) polyisocyanates may be selected from the group consisting of diphenylmethane diisocyanate ("MDI"), polymeric diphenylmethane diisocyanate ("pMDI"), toluene diisocyanate ("TDI"), hexamethylene diisocyanate ("HDI"), dicyclohexylmethane diisocyanate ("HMDI"), isophorone diisocyanate ("IPDI"), cyclohexyl diisocyanate ("CHDI"), naphthalene diisocyanate ("NDI"), phenyl diisocyanate ("PDI"), and combinations thereof. In one embodiment, the (B) polyisocyanate is of the formula OCN-R-NCO, where R is a hydrocarbon moiety (e.g., linear, cyclic, and / or aromatic moiety). In this embodiment, the (B) polyisocyanate can contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0032] Specific examples of suitable (B) polyisocyanates include alkylene diisocyanates having 4 to 12 carbons in the alkylene moiety, such as 1,12-dodecane diisocyanate, 2-ethyl-1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, and 1,6-hexamethylene diisocyanate; alicyclic diisocyanates, such as 1,3- and 1,4-cyclohexane diisocyanate, and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydro toluene diisocyanate and the corresponding isomeric mixtures, 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomeric mixtures, and aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomeric mixtures, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate and the corresponding isomeric mixtures, mixtures of 4,4'-, 2,4'-, and 2,2-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates, and mixtures of MDI and toluene diisocyanate (TDI).

[0033] (B) The polyisocyanate may include modified polyisocyanates, i.e., products obtained by partial chemical reaction of organic diisocyanates and / or polyisocyanates. Examples of suitable modified polyisocyanates include diisocyanates and / or polyisocyanates containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups, and / or urethane groups. Specific examples of suitable modified polyisocyanates include organic polyisocyanates containing urethane groups and having an NCO content of 15 to 33.6 parts by weight based on the total weight, such as low molecular weight diols, triols, dialkylene glycols, trialkylene glycols, or polyoxyalkylene glycols having a molecular weight of up to 6,000; modified 4,4'-diphenylmethane diisocyanate or 2,4- and 2,6-toluene diisocyanates; examples of di- and polyoxyalkylene glycols which may be used individually or in mixtures include diethylene glycol, dipropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene polyoxyethylene glycol or -triols. (B) Prepolymers containing NCO groups, having an NCO content of 3.5 to 29 parts by weight, based on the total weight of the polyisocyanate, produced from polyester polyols and / or polyether polyols; 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, or polymeric MDI are also suitable. Furthermore, liquid polyisocyanates containing carbodiimide groups, for example based on 4,4'- and 2,4'- and / or 2,2'-diphenylmethane diisocyanate and / or 2,4'- and / or 2,6-toluene diisocyanate, may also be suitable. The modified polyisocyanates may optionally be mixed together or with unmodified organic polyisocyanates such as 2,4'- and 4,4'-diphenylmethane diisocyanate, polymeric MDI, 2,4'- and / or 2,6-toluene diisocyanate.

[0034] It is to be understood that the (B) polyisocyanate may comprise any combination of two or more polyisocyanates that differ from one another based on functionality, molecular weight, viscosity, or structure. In a specific embodiment, the (B) polyisocyanate comprises, consists essentially of, or is MDI, which may include any blend of its isomers.

[0035] (B) The polyisocyanate typically has a functionality from 2.0 to 5.0, alternatively from 2.0 to 4.5, alternatively from 2.0 to 4.0, alternatively from 2.0 to 3.5.

[0036] In these or other embodiments, the (B) polyisocyanate has an NCO content by weight of 15 to 60 weight percent, alternatively 15 to 55 weight percent, alternatively 20 to 48.5 weight percent. Methods for determining the NCO content by weight are known in the art, based on the functionality and molecular weight of the particular isocyanate.

[0037] In certain embodiments, the composition comprises component (B) in an amount of from greater than 0 to 75 weight percent, alternatively from 10 to 50 weight percent, alternatively from 10 to 40 weight percent, or alternatively from 10 to 30 weight percent, based on the total weight of the composition.

[0038] (A) carbinol-functional siloxanes are not prepared by hydrosilylation reactions, and further, the composition contains less than 5 mole%, alternatively less than 4.5 mole%, alternatively less than 4 mole%, alternatively less than 3.5 mole%, alternatively less than 3 mole%, alternatively less than 2.5 mole%, alternatively less than 2 mole%, alternatively less than 1.5 mole%, alternatively less than 1 mole%, alternatively less than 0.5 mole%, alternatively 0 mole% of (C) a compound of formula RO a -(C b H 2b O) c -R 1 wherein R is an ethylenically unsaturated group and R 1is H or a hydrocarbyl group, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 at each moiety represented by subscript c, subscript c is 0 to 500, with the proviso that subscripts a and c are not simultaneously 0. The same explanations above regarding subscripts a, b, and c also apply to component (C). 1 With respect to the above, examples of hydrocarbyl groups include R 2 As described above.

[0039] The ethylenically unsaturated groups represented by R can be alkenyl and / or alkynyl groups having 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, or alternatively 2 carbon atoms. "Alkenyl" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, and hexenyl. "Alkynyl" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethynyl, propynyl, and butynyl. Various examples of ethylenically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-,

number

[0040] Conventional carbinol-functional siloxanes are prepared by hydrosilylation reactions in which an organopolysiloxane having silicon-bonded hydrogen atoms is hydrosilylated with an alcohol or polyether having one terminal unsaturated group (i.e., component (C)) in the presence of a hydrosilylation catalyst. A molar excess of component (C) is generally utilized to ensure that no residual silicon-bonded hydrogen atoms remain that may have undesirable reactivity in applications involving the carbinol-functional siloxane. As a result, conventional carbinol-functional siloxanes are generally utilized as reaction products that include both conventional carbinol-functional siloxanes as well as residual amounts of component (C), which may often constitute about 30 mol% of the reaction product. In other words, component (C) is inherently present with the conventional carbinol-functional siloxanes prepared by hydrosilylation. Because the boiling point temperatures of conventional carbinol-functional siloxane and component (C) are similar, it is difficult and impractical to purify conventional carbinol-functional siloxane by removing residual amounts of component (C) from the reaction product, for example, by distillation or stripping, especially when conventional carbinol-functional siloxane is linear and has a DP of less than 50, 40, 30, or 20.Residual amounts of component (C) cause undesirable by-products and side reactions when conventional carbinol-functional siloxane is used, for example, in further reactions.For example, component (C) is generally monovalent, and therefore can react and serve as a chain terminator rather than a chain extender.

[0041] However, it has surprisingly been discovered that by preparing component (A) via a method other than hydrosilylation, the presence of residual amounts of component (C) can be minimized or eliminated. By using component (A) in a pure form, free of residual amounts of component (C), component (A) can be used to prepare, for example, urethane prepolymers, or polyurethanes, or other reaction products having improved performance properties. In one embodiment, component (A) is: i) treating an aldehyde-functional siloxane under conditions that catalyze the hydroformylation reaction; (I) a gas containing hydrogen and carbon monoxide; (II) an alkenyl-functional siloxane; and (III) forming an aldehyde-functional siloxane by a process comprising combining starting materials comprising a rhodium / bisphosphite ligand complex catalyst; Optionally, ii) recovering the aldehyde-functional siloxane; and iii) combining starting materials including an aldehyde-functional siloxane, hydrogen, and a hydrogenation catalyst under conditions to catalyze the hydrogenation reaction, thereby forming a hydrogenation reaction product including a carbinol-functional siloxane; Optionally, iv) recovering the carbinol-functional siloxane; and Optionally, v) reacting a carbinol-functional siloxane, an alkylene oxide, and an alkoxylation catalyst under conditions to catalyze an alkoxylation reaction. to form a hydrogenated reaction product therefrom comprising a carbinol-functional siloxane in the form of a polyether-functional siloxane; Optionally, vi) recovering the carbinol-functional siloxane in the form of a polyether-functional siloxane.

[0042] The hydroformylation process described herein employs starting materials comprising (I) a gas comprising hydrogen and carbon monoxide, (II) an alkenyl-functional organosilicon compound, and (III) a rhodium / bisphosphite ligand catalyst. The starting materials may optionally further comprise (IV) a solvent.

[0043] The gas starting material (I) used in the hydroformylation process includes carbon monoxide (CO) and hydrogen gas (H2). For example, the gas can be synthesis gas. As used herein, "syngas" (from synthesis gas) refers to a gas mixture containing various amounts of CO and H2. Production methods are well known and include, for example, (1) steam reforming and partial oxidation of natural gas or liquid hydrocarbons, and (2) gasification of coal and / or biomass. CO and H2 are typically the major components of synthesis gas, but synthesis gas can contain carbon dioxide and inert gases such as CH4, N2, and Ar. The molar ratio of H2 to CO (H2:CO molar ratio) varies widely but can range from 1:100 to 100:1, alternatively 1:10 to 10:1. Synthesis gas is commercially available and is often used as a fuel source or as an intermediate for producing other chemicals. Alternatively, CO and H2 from other sources (i.e., other than syngas) may be used as starting material (I) herein. Alternatively, the H2:CO molar ratio in starting material (A) for use herein may be 3:1 to 1:3, alternatively 2:1 to 1:2, alternatively 1:1.

[0044] The alkenyl-functional siloxane starting material (II) is selected based on the desired structure of component (A). The only difference between starting material (II) and component (A) is that the alkenyl functionality of starting material (II) is ultimately converted to a carbinol functionality, but the structure of the siloxane itself is otherwise the same.

[0045] The starting material (III), a hydroformylation reaction catalyst for use in the process for making aldehyde-functional siloxanes, comprises an active complex of rhodium and a closed-end bisphosphite ligand. The bisphosphite ligand may be symmetric or asymmetric. Alternatively, the bisphosphite ligand may be symmetric. The bisphosphite ligand is represented by the formula (i):

[0046] [ka] (In the formula, R 6 and R 6’ are each independently selected from the group consisting of hydrogen, an alkyl group of at least one carbon atom, a cyano group, a halogen group, and an alkoxy group of at least one carbon atom; R 7 and R 7’ are each independently an alkyl group of at least 3 carbon atoms, and a group of the formula -SiR 17 3 groups, wherein each R 17 is an independently selected monovalent hydrocarbon radical of 1 to 20 carbon atoms; R 8 , R 8’ , R 9 , and R 9’ are each independently selected from the group consisting of hydrogen, an alkyl group, a cyano group, a halogen group, and an alkoxy group; R 10 , R 10’ , R 11 , and R 11’ are each independently selected from the group consisting of hydrogen and alkyl groups. 7 and R 7’ One of the groups may be hydrogen.

[0047] In formula (i), R 6 and R 6’ R can be an alkyl group of at least 1 carbon atom, alternatively 1 to 20 carbon atoms. 6 and R 6’ Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 20 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 6 and R 6’The alkyl groups of R may be selected from the group consisting of ethyl, propyl, and butyl, or propyl and butyl. 6 and R 6’ The alkyl group in R may be butyl. 6 and R 6’ may be an alkoxy group, the alkoxy group being of the formula -OR 6’’ wherein R 6’’ is R 6 and R 6 ' is an alkyl group as described above.

[0048] Alternatively, in formula (i), R 6 and R 6’ may be independently selected from alkyl groups of 1 to 6 carbon atoms and alkoxy groups of 1 to 6 carbon atoms. 6 and R 6’ can be an alkyl group of 2 to 4 carbon atoms. Alternatively, R 6 and R 6’ may be an alkoxy group of 1 to 4 carbon atoms. 6 and R 6’ may be a butyl group or a tert-butyl group. Alternatively, R 6 and R 6’ can be a methoxy group.

[0049] In formula (i), R 7 and R 7’ R can be an alkyl group of at least 3 carbon atoms, alternatively 3 to 20 carbon atoms. 7 and R 7’Suitable alkyl groups for may be linear, branched, cyclic, or a combination of two or more thereof. The alkyl groups are exemplified by propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobutyl), pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 20 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, R 7 and R 7’ The alkyl group of R may be selected from the group consisting of propyl and butyl. 7 and R 7’ The alkyl group can be butyl.

[0050] Alternatively, in formula (i), R 7 and R 7’ is represented by the formula -SiR 17 3 silyl groups, where each R 17 is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms. The monovalent hydrocarbon group is 6 and R 6 can be an alkyl group of 1 to 20 carbon atoms as described above.

[0051] Alternatively, in formula (i), R 7 and R 7’ may each be an independently selected alkyl group or an alkyl group of 3 to 6 carbon atoms. 7 and R 7’ can be an alkyl group of 3 to 4 carbon atoms. Alternatively, R 7 and R 7’ may be a butyl group, alternatively a tert-butyl group.

[0052] In formula (i), R 8 , R 8’ , R 9 , R 9’ is R 6 and R6’ Alternatively, R may be an alkyl group of at least one carbon atom as described above for 8 and R 8’ may be independently selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms. 8 and R 8’ Alternatively, in formula (i), R 9, and R 9’ may be independently selected from the group consisting of hydrogen and alkyl groups of 1 to 6 carbon atoms. 9 and R 9’ can be hydrogen.

[0053] In formula (i), R 10 and R 10’ R can be a hydrogen atom or an alkyl group of at least one carbon atom or from 1 to 20 carbon atoms. 10 and R 10’ The alkyl group of R 6 and R 6 ' may be as described above. Alternatively, R 10 and R 10’ Alternatively, R 10 and R 10’ can be hydrogen.

[0054] In formula (i), R 11 and R 11’ R can be a hydrogen atom, or an alkyl group of at least one carbon atom, or an alkyl group of 1 to 20 carbon atoms. 11 and R 11’ The alkyl group of R 6 and R 6 ' may be as described above. Alternatively, R 11 and R 11’ can be hydrogen.

[0055] Alternatively, the ligand of formula (i) may be selected from the group consisting of: (C1-1) 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepine; (C1-2) 6,6'-[(3,3'-di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepine); and a combination of both (C1-1) and (C1-2).

[0056] Alternatively, the ligand may include 6,6'-[[3,3',5,5'-tetrakis(1,1-dimethylethyl)-1,1'-biphenyl]-2,2'-diyl]bis(oxy)]bis-dibenzo[d,f][1,3,2]dioxaphosphepine, as disclosed in column 11 of U.S. Pat. No. 10,023,516 (see also U.S. Pat. No. 7,446,231, which discloses this compound as Ligand D in column 22, and U.S. Pat. No. 5,727,893, which discloses this compound as Ligand F in column 20, lines 40-60).

[0057] Alternatively, the ligand may include biphephos, commercially available from Sigma Aldrich, and may be prepared as described in U.S. Patent No. 9,127,030. (See also U.S. Patent No. 7,446,231, column 21 for Ligand B, and U.S. Patent No. 5,727,893, column 20, lines 5-18 for Ligand D).

[0058] The rhodium / bisphosphite ligand complex catalyst starting material (III) can be prepared by methods known in the art, such as those disclosed in U.S. Patent No. 4,769,498 to Billig et al., column 20, line 50 to column 21, line 40, and U.S. Patent No. 10,023,516 to Brammer et al., column 11, line 35 to column 12, line 12, by varying the appropriate starting materials. For example, the rhodium / bisphosphite ligand complex can be prepared by a process comprising combining a rhodium precursor with the above-mentioned bisphosphite ligand (i) under conditions to form a complex, which can then be introduced into a hydroformylation reaction medium containing one or both of the above-mentioned starting materials (I) and / or (II). Alternatively, for in situ formation of the rhodium / bisphosphite ligand complex, the rhodium / bisphosphite ligand complex may be formed in situ by introducing a rhodium catalyst precursor to the reaction medium and (i) introducing a bisphosphite ligand to the reaction medium (e.g., before, during, and / or after introduction of the rhodium catalyst precursor). The rhodium / bisphosphite ligand complex may be activated by heating and / or exposure to starting material (I) to form (III) the rhodium / bisphosphite ligand complex catalyst. The rhodium catalyst precursor may be rhodium dicarbonyl acetylacetonate, RhO 3、 Rh4(CO) 12 , Rh6(CO) 16 , and Rh(NO3)3.

[0059] For example, the rhodium precursor, such as rhodium dicarbonyl acetylacetonate, optionally the starting material (IV), the solvent, and (i) the bisphosphite ligand may be combined by any convenient means, such as, for example, by mixing. The resulting rhodium / bisphosphite ligand complex may be introduced into a reactor, optionally with an excess of the bisphosphite ligand. Alternatively, the rhodium precursor, (IV) the solvent, and the bisphosphite ligand may be combined with the starting material (I) and / or (II), the alkenyl functional siloxane, in the reactor, and the rhodium / bisphosphite ligand complex may be formed in situ. The relative amounts of the bisphosphite ligand and the rhodium precursor are sufficient to provide a molar ratio of bisphosphite ligand / Rh of 10 / 1 to 1 / 1, alternatively 5 / 1 to 1 / 1, alternatively 3 / 1 to 1 / 1, alternatively 2.5 / 1 to 1.5 / 1. In addition to the rhodium / bisphosphite ligand complex, excess (e.g., uncomplexed) bisphosphite ligand may be present in the reaction mixture. The excess bisphosphite ligand may be the same as or different from the bisphosphite ligand in the complex.

[0060] The amount of (III) rhodium / bisphosphite ligand complex catalyst (catalyst) is sufficient to catalyze the hydroformylation of (II) alkenyl-functional siloxane. The exact amount of catalyst will vary depending on a variety of factors, including the type of alkenyl-functional siloxane selected for the starting material (II), its exact alkenyl content, and reaction conditions such as temperature and pressure of the starting material (I). However, the amount of (III) hydroformylation reaction catalyst may be sufficient to provide a rhodium metal concentration of at least 0.1 ppm, alternatively 0.15 ppm, alternatively 0.2 ppm, alternatively 0.25 ppm, or alternatively 0.5 ppm, based on the weight of (II) alkenyl-functional siloxane. At the same time, the amount of (III) hydroformylation reaction catalyst may be sufficient to provide a rhodium metal concentration of up to 300 ppm, alternatively up to 100 ppm, alternatively up to 20 ppm, or alternatively up to 5 ppm, based on the same basis. Alternatively, the amount of (III) hydroformylation catalyst can be sufficient to provide from 0.1 ppm to 300 ppm, alternatively from 0.2 ppm to 100 ppm, alternatively from 0.25 ppm to 20 ppm, alternatively from 0.5 ppm to 5 ppm, based on the weight of the (II) alkenyl-functional siloxane.

[0061] The hydroformylation process reaction may be carried out without an additional solvent. Alternatively, the hydroformylation process reaction may be carried out with a solvent.

[0062] In the processes described herein, step 1) is carried out at a relatively low temperature. For example, step 1) may be carried out at a temperature of at least 30°C, alternatively at least 50°C, alternatively at least 70°C. At the same time, the temperature in step 1) may be up to 150°C, alternatively up to 100°C, alternatively up to 90°C, alternatively up to 80°C. Without being bound by theory, it is believed that lower temperatures, e.g., 30°C-90°C, alternatively 40°C-90°C, alternatively 50°C-90°C, alternatively 60°C-90°C, alternatively 70°C-90°C, alternatively 80°C-90°C, alternatively 30°C-60°C, alternatively 50°C-60°C, may be desired to obtain high selectivity and ligand stability.

[0063] In the processes described herein, step 1) may be carried out at a pressure of at least 101 kPa (ambient pressure), alternatively at least 206 kPa (30 psi), alternatively at least 344 kPa (50 psi). At the same time, the pressure in step 1) may be up to 6,895 kPa (1,000 psi), alternatively up to 1,379 kPa (200 psi), alternatively up to 1000 kPa (145 psi), alternatively up to 689 kPa (100 psi). Alternatively, step 1) may be carried out at 101 kPa to 6,895 kPa, alternatively from 344 kPa to 1,379 kPa, alternatively from 101 kPa to 1,000 kPa, alternatively from 344 kPa to 689 kPa. Without being bound by theory, it is believed that it may be beneficial to use relatively low pressures in the processes herein, e.g., <6,895 kPa, and the ligands described herein enable low pressure hydroformylation processes, which have the benefits of lower cost and better safety than high pressure hydroformylation processes.

[0064] The hydroformylation process may be carried out in batch, semi-batch, or continuous mode using one or more suitable reactors, such as fixed bed reactors, fluidized bed reactors, continuous stirred tank reactors (CSTRs), or slurry reactors. (II) The alkenyl-functional siloxane compound and (III) the selection of the hydroformylation reaction catalyst, and (IV) whether a solvent is used, may affect the size and type of reactor used. One reactor, or two or more different reactors may be used. The hydroformylation process may be carried out in one or more steps, which may be influenced by balancing capital costs, achieving high catalyst selectivity, activity, life, and ease of operation, as well as the reactivity of the particular starting material and the reaction conditions selected, and the desired products.

[0065] Alternatively, the hydroformylation process can be carried out in a continuous manner. For example, the process used can be as described in U.S. Patent No. 10,023,516, except that the olefin feed stream and catalyst described therein are replaced with (II) the alkenyl-functional siloxane and (III) the rhodium / bisphosphite ligand complex catalyst described herein, respectively.

[0066] Step 1) of the hydroformylation process forms a reaction fluid containing aldehyde-functional siloxanes. The reaction fluid may further include additional materials, such as those intentionally used during step 1) of the process or those formed in situ. Examples of such materials that may also be present include unreacted (II) alkenyl-functional siloxanes, unreacted (I) carbon monoxide and hydrogen gas, and / or by-products formed in situ, such as ligand decomposition products and their adducts, and high-boiling liquid aldehyde condensation by-products, and (IV) solvents, if used. The term "ligand decomposition products" includes, but is not limited to, any and all compounds resulting from one or more chemical transformations of at least one of the ligand molecules used in the process.

[0067] The hydroformylation process may further include one or more additional steps, such as 2) recovering the (III) rhodium / bisphosphite ligand complex catalyst from the reaction fluid containing the aldehyde-functional siloxane. Recovering the (III) rhodium / bisphosphite ligand complex catalyst may be carried out by methods known in the art, including, but not limited to, adsorption and / or membrane separation (e.g., nanofiltration). Suitable recovery methods are described, for example, in U.S. Patent No. 5,681,473 to Miller et al., U.S. Patent No. 8,748,643 to Priske et al., and U.S. Patent No. 10,155,200 to Geilen et al.

[0068] However, one benefit of the process described herein is that it is not necessary to remove and reuse (III) hydroformylation catalyst.Due to the low level of Rh required, it may be more cost-effective not to recover and reuse (III) hydroformylation catalyst, and the aldehyde-functional siloxane produced by the process may be stable even if the hydroformylation catalyst is not removed.Furthermore, without being bound by theory, it is believed that (III) hydroformylation catalyst may also catalyze the hydrogenation reaction of aldehyde-functional siloxane to form carbinol-functional siloxane, as described herein below.Therefore, alternatively, the above hydroformylation process may be carried out without step 2).

[0069] Alternatively, the hydroformylation process may further include 3) purification of the reaction product.For example, the aldehyde-functional siloxane may be isolated from the above additional materials by any convenient means, such as stripping and / or distillation, optionally using reduced pressure.Alternatively, step 3) may be omitted, for example, to leave the (III) hydroformylation catalyst in the hydroformylation reaction product containing the aldehyde-functional siloxane.

[0070] Aldehyde-functional siloxanes are useful as starting materials in the above process for preparing carbinol-functional siloxanes. The starting material (V) is an aldehyde-functional siloxane having at least one aldehyde functional group covalently bonded to silicon per molecule. Alternatively, the aldehyde-functional siloxane may have two or more aldehyde functional groups covalently bonded to silicon per molecule. The aldehyde functional group covalently bonded to silicon is represented by the formula:

[0071] [ka] where G is a divalent hydrocarbon group free of aliphatic unsaturation having 2 to 8 carbon atoms. G may be linear or branched. Examples of divalent hydrocarbyl groups for G include those having the empirical formula -C r H 2r -, where the subscript r is 2 to 8. The alkane-diyl group can be a linear alkane-diyl, for example, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-CH2-, or -CH2-CH2-CH2-CH2-CH2-CH2-CH2-, or a branched alkane-diyl, for example,

[0072] [ka] Alternatively, each G can be an alkane-diyl group of 2 to 6 carbon atoms, alternatively 2, 3, or 6 carbon atoms.

[0073] The process for preparing the carbinol functional siloxane comprises: I) under conditions which catalyze a hydrogenation reaction, (V) the aldehyde-functional siloxane described above; (VI) hydrogen; (VII) combining a starting material comprising a hydrogenation catalyst, thereby forming a hydrogenated reaction product comprising the carbinol-functional siloxane.

[0074] The process may optionally further comprise, prior to step I), i) combining starting materials comprising (I) a gas comprising hydrogen and carbon monoxide, (II) an alkenyl-functional siloxane, and (III) a rhodium / bisphosphite ligand complex catalyst under conditions to catalyze the hydroformylation reaction, thereby forming a hydroformylation reaction product comprising an aldehyde-functional siloxane as described above. The method may optionally further comprise, prior to step I) and after step i), ii) recovering the (III) rhodium / bisphosphite ligand complex catalyst from the reaction product comprising the aldehyde-functional siloxane. The process may optionally further comprise, prior to step I) and after step i), iii) purifying the reaction product, thereby isolating the aldehyde-functional siloxane from additional materials as described above.

[0075] Hydrogen is known in the art and is commercially available from a variety of sources, including Air Products (Allentown, Pennsylvania, USA). Hydrogen may be used in superstoichiometric amounts relative to the aldehyde-functionality of the starting material (V) aldehyde-functional siloxane described above to allow complete hydrogenation.

[0076] The hydrogenation catalyst used in the process for preparing carbinol-functional siloxanes can be a heterogeneous hydrogenation catalyst, a homogeneous hydrogenation catalyst, or a combination thereof. Alternatively, the hydrogenation catalyst can be a heterogeneous hydrogenation catalyst. Suitable heterogeneous hydrogenation catalysts include metals selected from the group consisting of cobalt (Co), copper (Cu), nickel (Ni), palladium (Pd), platinum (Pt), ruthenium (Ru), and combinations of two or more thereof. Alternatively, the hydrogenation catalyst can include Co, Cu, Ni, Pd, or combinations of two or more thereof. Alternatively, the hydrogenation catalyst can include Co, Cu, Ni, or combinations of two or more thereof. The hydrogenation catalyst can include a support such as alumina (Al2O3), silica (SiO2), silicon carbide (SiC), or carbon (III). Alternatively, the hydrogenation catalyst may be selected from the group consisting of Raney nickel, Raney copper, Ru / C, Ru / Al2O3, Pd / C, Pd / Al2O3, Cu / C, Cu / Al2O3, Cu / SiO2, Cu / SiC, Cu / C, and combinations of two or more thereof.

[0077] Alternatively, the heterogeneous hydrogenation catalyst for the hydrogenation of aldehydes may comprise copper, chromium, nickel, or a support material to which two or more of these are applied as active components. Exemplary catalysts include 0.3-15% copper, 0.3%-15% nickel, and 0.05%-3.5% chromium. The support material may be, for example, porous silicon dioxide or aluminum oxide. Barium may optionally be added to the support material. Alternatively, a chromium-free hydrogenation catalyst may be used. For example, Ni / Al2O3 or Co / Al2O3, or a copper oxide / zinc oxide-containing catalyst (which may further comprise potassium, nickel, and / or cobalt), plus an alkali metal, may be used. Suitable hydrogenation catalysts are disclosed, for example, in U.S. Pat. No. 7,524,997 or U.S. Pat. No. 9,567,276 and references cited therein.

[0078] Examples of heterogeneous hydrogenation catalysts suitable for use herein include Raney nickel, e.g., Raney nickel 2400, Ni-3288, Raney copper, Hysat 401 salt (Cu), ruthenium on carbon (Ru / C), platinum on carbon (Pt / C), copper on silicon carbide (Cu / SiC).

[0079] Alternatively, homogeneous hydrogenation catalysts may be used herein. The homogeneous hydrogenation catalyst may be a metal complex, and the metal may be selected from the group consisting of Co, Fe, Ir, Rh, and Ru. Examples of suitable homogeneous hydrogenation catalysts are [RhCl(PPh3)3] (Wilkinson's catalyst), [Rh(NBD)(PR'3)2]+ClO4- (where R' is an alkyl group, e.g., Et), [RuCl2(diphosphine)(1,2-diamine)] (Noyori's catalyst), RuCl2(TRIPHOS) (where TRIPHOS = PhP[(CH2CH2PPh2)2], Ru(II)(dppp)(glycine) complex (where dppp = 1,3-bis(diphenylphosphino)propane), RuCl2(PPh3), RuCl2(CO)2(PPh3), IrH3(PPh3), [Ir(H2)(CH3COO)(PPh3)], cis-[Ru-Cl2(ampy)(PP)] [where ampy = 2-(aminomethyl)pyridine, and PP = 1,4-bis-(diphenylphosphino)butane, 1,1'-ferrocenediyl-bis(diphenylphosphine)], pincer RuCl(CNNR)(PP) complexes [where PP = 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-ferrocenediyl-bis(diphenylphosphine)] and HCNNR = 4-substituted aminomethyl-benzo[h]quinolines, R = Me, Ph], [RuCl(dppb)(ampy)] (where dppb = 1,4-bis(diphenylphosphino)butane, ampy = 2-aminomethylpyridine), [Fe(PNPMeiPr)(CO)(H)(Br)], [Fe(PNPMe-iPr)(H)2(CO)], and combinations thereof.

[0080] The amount of hydrogenation catalyst used in the process varies depending on various factors including whether the process is run in batch or continuous mode, the selection of the aldehyde-functional siloxane, whether a heterogeneous or homogeneous hydrogenation catalyst is selected, and reaction conditions such as temperature and pressure. However, when the process is run in batch mode, the amount of catalyst can be 1% to 20% by weight, alternatively 5% to 10% by weight, based on the weight of the aldehyde-functional siloxane. Alternatively, the amount of catalyst can be at least 1, alternatively at least 4, alternatively at least 6.5, alternatively at least 8% by weight, while the amount of catalyst can be up to 20, alternatively up to 14, alternatively up to 13, alternatively up to 10, alternatively up to 9% by weight, on the same basis. Alternatively, when the process is run in continuous mode, for example by packing the heterogeneous hydrogenation catalyst in a fixed bed reactor, the amount of hydrogenation catalyst can be up to 10 hr. -1 Reactor volume (filled with hydrogenation catalyst) to achieve a space time of 1 m 2 The catalyst surface area may be sufficient to achieve 10 kg / hr of substrate per sintered material.

[0081] The solvent that may be optionally used in the process for the hydrogenation reaction may be selected from solvents that are neutral to the reaction. The following are specific examples of such solvents: monohydric alcohols such as ethanol and isopropyl alcohol; ethers such as dioxane, THF; aliphatic hydrocarbons such as hexane, heptane, and paraffinic solvents; and aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons, and water. These solvents may be used individually or in combination of two or more.

[0082] The hydrogenation reaction may be carried out using pressurized hydrogen. The hydrogen (gauge) pressure may be from 10 psig (68.9 kPa) to 3000 psig (20684 kPa), alternatively from 10 psig to 2000 psig (13790 kPa), alternatively from 10 psig to 800 psig (5516 kPa), alternatively from 50 psig (345 kPa) to 200 psig (1379 kPa). The reaction may be carried out at a temperature of 0 to 200° C. Alternatively, to shorten the reaction time, a temperature of 50 to 150° C. may be suitable. Alternatively, the hydrogen (gauge) pressure used may be at least 25, alternatively at least 50, alternatively at least 100, alternatively at least 150, alternatively at least 164 psig, while the hydrogen gauge pressure may be up to 800, alternatively up to 400, alternatively up to 300, alternatively up to 200, alternatively up to 194 psig. The temperature for the hydrogenation reaction may be at least 50, alternatively at least 65, alternatively at least 80°C, while the temperature may be up to 200, alternatively up to 150, alternatively up to 120°C.

[0083] The hydrogenation reaction can be carried out as a batch process or as a continuous process. In a batch process, the hydrogenation reaction can be carried out for 1 minute to 24 hours, although the reaction time varies depending on various factors including the amount of catalyst and the reaction temperature. Alternatively, the hydrogenation reaction can be carried out for at least 1 minute, alternatively at least 2 minutes, alternatively at least 1 hour, alternatively at least 2.5 hours, alternatively at least 3 hours, alternatively at least 3.3 hours, alternatively at least 3.7 hours, alternatively at least 4 hours, alternatively at least 4.4 hours, alternatively at least 5.5 hours, while the hydrogenation reaction can be carried out for up to 24 hours, alternatively up to 22.5 hours, alternatively up to 22 hours, alternatively up to 12 hours, alternatively up to 7 hours, alternatively up to 6 hours.

[0084] Alternatively, in a batch process, the end point of the hydrogenation reaction may be considered to be the time when no further decrease in hydrogen pressure is observed after continuing the reaction for another 1-2 hours. If the hydrogen pressure decreases during the course of the reaction, it may be desirable to repeat the introduction of hydrogen and maintain it under elevated pressure to shorten the reaction time. Alternatively, the reactor may be repressurized with hydrogen one or more times to achieve a sufficient supply of hydrogen for the reaction of the aldehyde while maintaining a reasonable reactor pressure.

[0085] After completion of the hydrogenation reaction, the hydrogenation catalyst may be separated by any convenient means, such as filtration or adsorption, for example with diatomaceous earth or activated carbon, sedimentation, centrifugation, in a pressurized inert (e.g., nitrogen) atmosphere, by maintaining the catalyst in structured packing or other fixed structure, or by a combination of these.

[0086] The carbinol-functional siloxanes prepared as described above have at least one carbinol functional group covalently bonded to silicon per molecule. Alternatively, the carbinol-functional siloxanes may have two or more carbinol functional groups covalently bonded to silicon per molecule. The carbinol functional group covalently bonded to silicon, R Car is the expression:

[0087] [ka] where G is a divalent hydrocarbon radical free of aliphatic unsaturation having 2 to 8 carbon atoms, as described and exemplified above. Examples of carbinol-functional siloxanes prepared by this process are as described and exemplified above.

[0088] Starting material (IV) is a solvent that can be optionally used in the method for making polyether-functional siloxane. Solvent can be added to facilitate mixing and / or delivery of one or more of the above starting materials. For example, (II) halogenated triarylborane Lewis acid can be delivered in a solvent. Alternatively, (III) carbinol-functional siloxane can be delivered in a solvent, for example, when the carbinol-functional siloxane comprises a carbinol-functional polyorganosiloxane resin.

[0089] Suitable solvents include those that do not react with the starting materials used in step (1). Solvents for use in step (1) include liquid hydrocarbons. For example, the hydrocarbon solvent can be an aromatic hydrocarbon such as benzene, ethylbenzene, toluene, xylene, or an aliphatic hydrocarbon such as heptane, or a combination of both aromatic and aliphatic hydrocarbons. Alternatively, the solvent can include liquid non-functional siloxanes such as low viscosity linear and cyclic polydiorganosiloxanes. The amount of solvent is not critical and will vary depending on a variety of factors including whether (III) the carbinol-functional siloxane is solid under ambient conditions (e.g., carbinol-functional polyorganosiloxane resins) and the type of reactor selected for alkoxylation. However, the amount of solvent used during the alkoxylation reaction in step (1) can be from 1% to 90% by weight based on the combined weight of (I) the epoxide, (II) the halogenated triarylborane Lewis acid, and (III) the carbinol-functional siloxane.

[0090] When the carbinol functional group of component (A) is a polyether group, the method of preparing component (A) can further include combining starting materials comprising a carbinol-functional siloxane, an alkylene oxide, and an alkoxylation catalyst under conditions to catalyze an alkoxylation reaction to form therefrom a hydrogenation reaction product comprising the carbinol-functional siloxane in the form of a polyether-functional siloxane.

[0091] The alkylene oxide, if present, is selected based on the desired structure of the polyether group of component (A). The alkylene oxide can be, for example, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, decylene oxide, or a combination of two or more thereof.

[0092] Additional instructions for preparing component (A) are disclosed in 84744-US-PSP, which is incorporated herein by reference in its entirety.

[0093] In certain embodiments, the composition further comprises a (D) polyol. In a specific embodiment, the (D) polyol comprises or alternatively consists of a polyether polyol. Suitable polyether polyols for the composition include, but are not limited to, products obtained by polymerization of cyclic oxides, such as ethylene oxide ("ethylene oxide, EO"), propylene oxide ("propylene oxide, PO"), butylene oxide ("butylene oxide, BO"), tetrahydrofuran, or epichlorohydrin, in the presence of a multifunctional initiator. Suitable initiators contain two or more, i.e., multiple, active hydrogen atoms. Catalysis for this polymerization can be either anionic or cationic, and suitable catalysts include KOH, CsOH, boron trifluoride, or double metal cyanide complex (DMC) catalysts, such as zinc hexacyanocobaltate or quaternary phosphazenium compounds. Initiators include, for example, neopentyl glycol; 1,2-propylene glycol; water and trimethylolpropane; pentaerythritol; sorbitol; sucrose; glycerol; amino alcohols such as ethanolamine, diethanolamine, and triethanolamine; 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,2-propanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,5-cyclohexanediol, 1,5-cyclohexanediol, 1,6-cyclohexanediol, 1,4-cyclohexanediol, 1,5 ... The initiator may be selected from alkanediols such as cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and / or 2,5-hexanediol; ethylene glycol, diethylene glycol, triethylene glycol, bis-3-aminopropylmethylamine; ethylenediamine; diethylenetriamine; 9(1)-hydroxymethyloctadecanol; 1,4-bishydroxymethylcyclohexane; hydrogenated bisphenols; 9,9(10,10)-bishydroxymethyloctadecanol; 1,2,6-hexanetriol; and combinations thereof. Other initiators include other linear and cyclic compounds containing amine groups.Exemplary polyamine initiators include ethylenediamine, neopentyldiamine, 1,6-diaminohexane; bisaminomethyltricyclodecane; bisaminocyclohexane; diethylenetriamine; bis-3-aminopropylmethylamine; triethylenetetramine; various isomers of toluenediamine; diphenylmethanediamine; N-methyl-1,2-ethanediamine, N-methyl-1,3-propanediamine; N,N-dimethyl-1,3-diaminopropane; N,N-dimethylethanolamine; 3,3'-diamino-N-methyldipropylamine; N,N-dimethyldipropylenetriamine; aminopropyl-imidazole; and combinations thereof. As understood in the art, the initiator compound or combinations thereof are generally selected based on the desired functionality of the resulting polyether polyol.

[0094] Other suitable polyether polyols include polyether diols and triols, such as polyoxypropylene diols and triols, and poly(oxyethylene-oxypropylene) diols and triols obtained by simultaneous or sequential addition of ethylene and propylene oxide to a difunctional or trifunctional initiator. Polyether polyols having higher functionality than the triols can also be used in place of or in addition to the polyether diols and / or triols. Copolymers having an oxyethylene content of 5 to 90% by weight, based on the weight of the copolymer, can be utilized. When the (D) polyol is a copolymer, the copolymer can be a block copolymer, a random / block copolymer, or a random copolymer. The (D) polyol can also be a terpolymer. Still other suitable polyether polyols include polytetramethylene glycol obtained by polymerization of tetrahydrofuran.

[0095] In other embodiments, the (D) polyol comprises or alternatively consists of a polyester polyol. Suitable polyester polyols for the composition include, but are not limited to, hydroxyl-functional reaction products of polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, glycerol, trimethylolpropane, pentaerythritol, sucrose, polyether polyols, including mixtures thereof, and polycarboxylic acids, especially dicarboxylic acids, or their ester-forming derivatives, such as succinic acid, glutaric acid, and adipic acid, or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, dimethyl terephthalate, or mixtures thereof. It is also possible to use polyester polyols obtained by polymerization of lactones, such as caprolactone, in combination with polyols, or polymerization of hydroxycarboxylic acids, such as hydroxycaproic acid. In certain embodiments, the (D) polyol comprises a mixture of polyester and polyether polyols.

[0096] Suitable polyesteramide polyols can be obtained by including amino alcohols such as ethanolamine in the polyesterification mixture. Suitable polythioether polyols include products obtained by condensing thiodiglycol either alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino alcohols, or amino carboxylic acids. Suitable polycarbonate polyols include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or tetraethylene glycol with diaryl carbonates, e.g., diphenyl carbonate, or phosgene. Suitable polyacetal polyols include those prepared by reacting glycols such as diethylene glycol, triethylene glycol, or hexanediol with formaldehyde. Other suitable polyacetal polyols can also be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers, and suitable polysiloxane polyols include polydimethylsiloxane diols and triols.

[0097] In a particular embodiment, (D) polyol is a polymer polyol. In a particular embodiment, the polymer polyol is a graft polyol. Graft polyol can also be referred to as graft dispersion polyol or graft polymer polyol. Graft polyol often includes one or more vinyl monomers, such as styrene monomers and / or acrylonitrile monomers, and the product obtained by in-situ polymerization of macromers, such as polyether polyols, in polyol, i.e., polymer particles.

[0098] In another embodiment, the polymer polyol is selected from polyharnstoff (PHD) polyols, polyisocyanate polyaddition (PIPA) polyols, and combinations thereof. PHD polyols are typically formed by the in-situ reaction of diisocyanates with diamines in the polyol to give a stable dispersion of polyurea particles. PIPA polyols are similar to PHD polyols, except that the dispersion is typically formed by the in-situ reaction of alkanolamines, instead of diamines, with diisocyanates to give a polyurethane dispersion in the polyol. In yet another embodiment, the polymer polyol comprises a copolymer polyol based on styrene-acrylonitrile (SAN).

[0099] It is to be understood that the (D) polyol utilized in the composition can include any combination of two or more polyols that differ from one another on the basis of functionality, molecular weight, viscosity, or structure.

[0100] In various embodiments, the (D) polyol has a hydroxyl (OH) number of greater than 10 to 120 mg KOH / g, alternatively 20 to 90 mg KOH / g, alternatively 30 to 80 mg KOH / g, alternatively 40 to 70 mg KOH / g, alternatively 50 to 60 mg KOH / g. The hydroxyl number can be measured via various techniques, such as according to ASTM D4274. In these or other embodiments, the (D) polyol has a number average molecular weight of 1,000 to 4,000 daltons, alternatively 1,250 to 3,000 daltons, alternatively 1,500 to 2,500 daltons, alternatively 1,750 to 2,250 daltons, alternatively 1,900 to 2,100 daltons. As will be readily appreciated in the art, the number average molecular weight can be measured via gel permeation chromatography (GPC).

[0101] In these or other embodiments, the (D) polyol has a functionality of 2 to 10, alternatively from 2 to 9, alternatively from 2 to 8, alternatively from 2 to 7, alternatively from 2 to 6, alternatively from 2 to 5, alternatively from 2 to 4, alternatively from 2 to 3, or alternatively from 2.

[0102] It should be understood that when the (D) polyol comprises a blend of two or more different polyols, the above properties may be based on the overall (D) polyol, i.e., based on averaging the properties of the individual polyols in the (D) polyol, or may relate to a specific polyol in the blend of polyols. Typically, these properties relate to the overall (D) polyol. In specific embodiments, the (D) polyol comprises, consists essentially of, or consists of one or more polyether polyols. In other words, in these embodiments, the (D) polyol typically does not include any polyols that are not polyether polyols. In these or other embodiments, the (D) polyol comprises or is a homopolymer diol and / or triol.

[0103] In certain embodiments, the composition comprises component (D) in an amount from greater than 0 to 80 weight percent, alternatively from 10 to 70 weight percent, alternatively from 20 to 60 weight percent, and alternatively from 30 to 50 weight percent, based on the total weight of the composition.

[0104] In certain embodiments, the composition further comprises an (E) catalyst which, when utilized, typically catalyzes the formation of urethane bonds upon reacting components (A) and (B), and optionally component (D), as described below.

[0105] In one embodiment, the (E) catalyst comprises a tin catalyst. Suitable tin catalysts include tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octanoate, tin(II) ethylhexanoate, and tin(II) laurate. In one embodiment, the (E) catalyst comprises dibutyltin dilaurate, which is a dialkyltin(IV) salt of an organic carboxylic acid. Specific examples of suitable organometallic catalysts, such as dibutyltin dilaurate, are commercially available from Evonik under the trade name DABCO™. The organometallic catalyst may also include other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate.

[0106] Other examples of suitable catalysts include iron (II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines such as tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine, tetraalkylammonium hydroxides including tetramethylammonium hydroxide, alkali metal hydroxides including sodium hydroxide and potassium hydroxide, alkali metal alkoxides including sodium methoxide and potassium isopropoxide, and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and / or a pendant OH group.

[0107] Further examples of other suitable catalysts, specifically trimerization catalysts, include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, N,N,N-trimethylisopropylamine / formate, and combinations thereof.

[0108] Still further examples of other suitable catalysts, specifically tertiary amine catalysts, include dimethylaminoethanol, dimethylaminoethoxyethanol, triethylamine, N,N,N',N'-tetramethylethylenediamine, triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane), N,N-dimethylaminopropylamine, N,N,N',N',N''-pentamethyldipropylenetriamine, tris(dimethylaminopropyl)amine, N,N-dimethylpiperazine, tetramethylimino-bis(propylamine), dimethylbenzylamine, trimethylamine, triethanolamine, dimethylaminoethanol ... amine, N,N-diethylethanolamine, N-methylpyrrolidone, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylamino-ethyl)ether, N,N-dimethylcyclohexylamine ("DMCHA"), N,N,N',N',N"-pentamethyldiethylenetriamine, 1,2-dimethylimidazole, 3-(dimethylamino)propylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and combinations thereof. The (E) catalyst may include a delayed action tertiary amine based on 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU"). Alternatively, or in addition, the (E) catalyst may include N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethylether and / or ethylenediamine. The tertiary amine catalyst may be further modified for use as a delayed action catalyst by adding approximately the same stoichiometric amount of phenol or an acidic proton-containing acid such as formic acid. Such delayed action catalysts are commercially available from Air Products and Evonik.

[0109] The (E) catalyst may be utilized as is or may be disposed in a carrier vehicle. Carrier vehicles are known in the art and are further described below as optional components of the composition. When a carrier vehicle is utilized to solubilize the (E) catalyst, the carrier vehicle may be referred to as a solvent. The carrier vehicle may be an isocyanate-reactive, e.g., alcohol-functional carrier vehicle such as dipropylene glycol.

[0110] (E) Catalyst may be utilized in various amounts, and one of ordinary skill in the art will readily understand how to determine a suitable amount or amounts of (E) Catalyst.

[0111] The composition may further comprise a chain extender. As is readily understood in the art, the chain extender typically contains two, but not more than two, isocyanate-reactive groups (or active hydrogen atoms). These isocyanate-reactive groups are typically in the form of hydroxyl, primary amino, secondary amino, or a mixture of two or more of these groups. The term "active hydrogen atoms" refers to hydrogen atoms that, due to their location in the molecule, are active according to the Zerewitinoff test as described by Kohler in J. Am. Chemical Soc., 49, 31-81 (1927). When the chain extender is a diol, the resulting product is a polyurethane. When the chain extender is a diamine or amino alcohol, the resulting product is a polyurea.

[0112] Chain extenders may be aliphatic, cycloaliphatic, or aromatic and are exemplified by diols, diamines, and aminoalcohols. Examples of difunctional chain extenders are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol and other pentanediols, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, other 2-ethyl-hexanediols, 1,6-hexanediol and other hexanediols, 2,2,4-trimethylpentane-1,3-diol, decanediol, dodecanediol, bisphenol A, hydrogenated bisphenol A, 1,4-cyclohexanediol, 1,4-bis(2-hydroxyethoxy)-cyclohexane, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(2-hydroxyethoxy)benzene, ester diol 204 (TCI Propanoic acid, 3-hydroxy-2,2-dimethylpropyl ester available from Agrochemicals America), N-methylethanolamine, N-methylisopropylamine, 4-aminocyclohexanol, 1,2-diaminoethane, 1,3-diaminopropane, diethylenetriamine, toluene-2,4-diamine, and toluene-1,6-diamine. Aliphatic compounds containing 2 to 8 carbon atoms are most typical. Amine chain extenders include, but are not limited to, ethylenediamine, monomethanolamine, and propylenediamine.

[0113] Commonly used linear chain extenders are generally diol, diamine, or aminoalcohol compounds characterized by having a molecular weight of 400 g / mole (or Daltons) or less. In this context, "linear" means that it does not contain any branching from tertiary carbons. Examples of suitable chain extenders are those represented by the following formula: HO-(CH2) t -OH, H2N-(CH2) t -NH2 and H2N-(CH2) t -OH, where the subscript t is typically 1 to 50.

[0114] One common chain extender is 1,4-butanediol ("butanediol" or "BDO"), which is represented by the following formula: HO-CH2CH2CH2CH2-OH. Other suitable chain extenders include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,6-hexanediol, 1,5-heptanediol, triethylene glycol, and combinations of two or more of these extenders.

[0115] Also suitable are cyclic chain extenders, which are generally diol, diamine or aminoalcohol compounds characterized by having a molecular weight of 400 g / mol or less. In this context, "cyclic" means a ring structure, typical ring structures including, but not limited to, 5-8 membered ring structures with hydroxyl alkyl branches.

[0116] In certain embodiments, the composition comprises a chain extender in an amount of from greater than 0 to 40 weight percent, alternatively from 10 to 50 weight percent, alternatively from 10 to 40 weight percent, alternatively from 10 to 30 weight percent, based on the total weight of the composition.

[0117] In certain embodiments, the composition further comprises a pH adjuster or stabilizer, specific examples of which include diethyl malonate, alkylphenol alkylate, paratoluenesulfonic acid isocyanate, benzoyl chloride, and orthoalkyl formate. If utilized, the pH adjuster or stabilizer is typically present in the composition in an amount of greater than 0 to 5 weight percent, alternatively greater than 0 to 4 weight percent, alternatively greater than 0 to 3 weight percent, alternatively greater than 0 to 2 weight percent, alternatively greater than 0 to 1 weight percent, alternatively greater than 0 to 0.8 weight percent, alternatively greater than 0 to 0.5 weight percent, based on the total weight of the composition.

[0118] Also disclosed is a urethane prepolymer comprising the reaction product of the composition as introduced above. By urethane prepolymer, it is meant that the urethane prepolymer comprises at least one urethane bond.

[0119] In certain embodiments, the urethane prepolymer is formed with a stoichiometric excess of isocyanate functional groups in component (B) relative to the total amount of isocyanate reactive groups present in the composition, such as the isocyanate reactive groups in components (A) and (D) (if utilized) and the isocyanate reactive groups present in the chain extender (if utilized). Alternatively, this can be referred to as reacting with an isocyanate index of greater than 100. In these embodiments, the urethane prepolymer is an isocyanate functional prepolymer, and has a backbone that includes both organic moieties from components (B) and (D), if utilized, and one or more siloxane moieties from component (A). Typically, in these embodiments, the isocyanate reactive groups (i.e., the OH groups of component (D), if present, and the carbinol functional groups of component (A)) are consumed in preparing the urethane prepolymer, such that the urethane prepolymer does not include any isocyanate reactive groups. The urethane prepolymer comprises urethane linkages from the reaction between components (A) and (B) (and optionally between components (B) and (D)). In a specific embodiment, the urethane prepolymer typically comprises, on average, at least two isocyanate functional groups.

[0120] As one specific illustrative example, when the urethane prepolymer is formed with a stoichiometric excess of isocyanate functional groups in component (B) relative to the total amount of isocyanate-reactive groups present in the composition, when component (B) is 4,4'-MDI, when no (D) polyol or chain extender is present, and when component (A) is linear and contains polyether functional groups at each end, the urethane prepolymer may have the following formula:

[0121] [ka]

[0122] As another specific illustrative example, when the urethane prepolymer is formed with a stoichiometric excess of isocyanate functional groups in component (B) relative to the total amount of isocyanate-reactive groups present in the composition, when component (B) is 4,4'-MDI, when component (D) is present and is a propylene oxide-based polyether diol, and when component (A) is linear and contains a polyether functional group at each end, the urethane prepolymer may have the formula:

[0123] [ka]

[0124] In another embodiment, the urethane prepolymer is formed by a stoichiometrically equivalent amount of isocyanate functional groups in composition (B) and the total amount of isocyanate reactive groups present in the composition, such as the isocyanate reactive groups in components (A) and (D) (if utilized), and the isocyanate reactive groups present in the chain extender (if utilized). In these embodiments, the resulting urethane prepolymer may contain at least one isocyanate functional group and at least one carbinol functional group.

[0125] The composition may be used to form a polyurethane instead of a urethane prepolymer. For example, the composition may be a polyurethane composition in which component (A) is used in combination with or in place of polyol (D). In such an embodiment, the composition may optionally further comprise an additive component. The additive component may be selected from the group of catalysts, plasticizers, crosslinkers, chain terminators, wetting agents, surface modifiers, surfactants, waxes, moisture scavengers, drying agents, viscosity reducing agents, toughening agents, dyes, pigments, colorants, flame retardants, mold release agents, antioxidants, compatibilizers, UV stabilizers, thixotropic agents, anti-aging agents, lubricants, coupling agents, rheology promoters, thickeners, flame retardants, smoke suppressants, antistatic agents, antimicrobial agents, and combinations thereof.

[0126] One or more of the additives can be present in any suitable weight percentage (wt%) of the composition, for example, 0.1% to 15%, 0.5% to 5%, or 0.1% or less, 1%, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% or more by weight of the composition. Those of skill in the art can readily determine suitable amounts of additives depending, for example, on the type of additive and the desired result. Certain optional additives are described in more detail below.

[0127] The urethane prepolymers are particularly suitable for a variety of end use applications in curable compositions, for example, they may be utilized in adhesives, which are also provided by the present disclosure.

[0128] The adhesive can include the urethane prepolymer in an amount of greater than 10 to 60 weight percent, alternatively 20 to 50 weight percent, alternatively 20 to 40 weight percent, based on the total weight of the adhesive.

[0129] The adhesive typically further comprises (F) a filler.

[0130] The (F) filler may be untreated, pretreated, or added in combination with an optional filler treating agent, described below, which when so added may treat the (F) filler in situ and / or prior to use. The (F) filler may be a single filler or a combination of two or more fillers differing in at least one characteristic, such as filler type, preparation method, treatment or surface chemistry, filler composition, filler shape, filler surface area, average particle size, and / or particle size distribution.

[0131] The shape and size of the (F) filler are also not particularly limited. For example, the (F) filler may be spherical, oblong, oval, irregular, and may be in the form of, for example, powder, fine powder, fiber, flake, chip, shaving, strand, scrim, wafer, wool, straw, particles, and combinations thereof. The size and shape are typically selected based on the type of (F) filler utilized and the end use application of the adhesive. In certain embodiments, the (F) filler has an average particle size or average maximum dimension of more than 0 to 500 microns, alternatively more than 0 to 450 microns, alternatively more than 0 to 400 microns, alternatively more than 0 to 350 microns, alternatively more than 0 to 300 microns, alternatively more than 0 to 250 microns, alternatively more than 0 to 200 microns, alternatively more than 0 to 150 microns, alternatively more than 0 to 100 microns. In certain embodiments, the (F) filler has an average particle size or average maximum dimension of from greater than 0 to 500 nanometers, alternatively from greater than 0 to 450 nanometers, alternatively from greater than 0 to 400 nanometers, alternatively from greater than 0 to 350 nanometers, alternatively from greater than 0 to 300 nanometers, alternatively from greater than 0 to 250 nanometers, alternatively from greater than 0 to 200 nanometers, alternatively from greater than 0 to 150 nanometers, alternatively from greater than 0 to 100 nanometers. Methods of measuring average particle size are known in the art, for example, via light scattering techniques such as dynamic light scattering.

[0132] Non-limiting examples of fillers that may function as reinforcing fillers include reinforcing silica fillers such as fumed silica, silica aerogel, silica xerogel, and precipitated silica. Fumed silica is known in the art and is commercially available, for example, fumed silica sold under the name CAB-O-SIL by Cabot Corporation (Massachusetts, USA).

[0133] Non-limiting examples of fillers that may function as extending or reinforcing fillers include quartz and / or crushed quartz, aluminum oxide, magnesium oxide, silica (e.g., fumed silica, ground silica, precipitated silica), hydrated magnesium silicate, magnesium carbonate, dolomite, silicone resins, wollastonite, soapstone, kaolinite, kaolin, mica, muscovite, phlogopite, halloysite (hydrated alumina silicate), aluminum silicate, sodium aluminosilicate, glass (e.g., fibers, beads or particles, including recycled glass from wind turbines or other sources), clay, magnetite, hematite, calcium carbonate, e.g., precipitated calcium carbonate, fumed calcium carbonate, and / or ground calcium carbonate, calcium sulfate, barium sulfate, calcium metasilicate, zinc oxide, talc, diatomaceous earth, iron oxide, clay, mica, chalk, titanium dioxide (titania), zirconia, sand, carbon black, graphite, anthracite, coal, lignite, charcoal, activated carbon ... charcoal, non-functional silicone resins, alumina, silver, metal powders, magnesium oxide, magnesium hydroxide, magnesium oxysulfate fiber, aluminum trihydrate, oxyhydrate, coated fillers, carbon fibers (including, for example, recycled carbon fibers from the aircraft and / or automotive industries), polyaramids such as chopped KEVLAR™ or Twaron™, nylon fibers, mineral fillers or pigments (e.g., titanium dioxide, non-hydrated, partially hydrated, or hydrated fluorides, chlorides, bromides, iodides, chromates, carbonates, hydroxides, phosphates, hydrogen phosphates, nitrates, oxides, and sodium, potassium, magnesium, calcium, and barium; zinc oxide, antimony pentoxide, antimony trioxide, beryllium oxide, chromium oxide, lithopone, boric acid or borates, such as zinc borate, barium metaborate, or aluminum borate, mixed metal oxides, such as vermiculite, bentonite, pumice, perlite, fly ash, clay, and silica gel;rice husk ash, ceramics and zeolites, metals such as aluminum flakes or powders, bronze powders, copper, gold, molybdenum, nickel, silver powders or flakes, stainless steel powders, tungsten, barium titanate, silica-carbon black composites, functionalized carbon nanotubes, cement, slate powders, pyrophyllite, sepiolite, zinc stannate, zinc sulfide), and combinations thereof. Alternatively, the extending or reinforcing filler may be selected from the group consisting of calcium carbonate, talc, and combinations thereof;

[0134] Extending fillers are known in the art and are commercially available, for example, ground silica sold under the name MIN-U-SIL by US Silica, Berkeley Springs, WV. Suitable precipitated calcium carbonates include Winnofil™ SPM from Solvay, and Ultra-pflex™ and Ultra-pflex™ 100 from SMI.

[0135] Alternatively, the (F) filler may be selected from the group consisting of aluminum nitride, aluminum oxide, aluminum hydroxide, aluminum trihydrate, barium titanate, barium sulfate, beryllium oxide, carbon fibers, diamond, graphite, magnesium hydroxide, magnesium oxide, magnesium oxysulfate fibers, metal particles, onyx, silicon carbide, tungsten carbide, zinc oxide, coated fillers, and combinations thereof.

[0136] Metal fillers include metal particles, metal powders, and metal particles having layers on the surface of the particles. These layers can be, for example, metal nitride layers or metal oxide layers. Suitable metal fillers are exemplified by particles of metals selected from the group consisting of aluminum, copper, gold, nickel, silver, and combinations thereof, alternatively aluminum. Suitable metal fillers are further exemplified by particles of the metals listed above having layers on their surface selected from the group consisting of aluminum nitride, aluminum oxide, copper oxide, nickel oxide, silver oxide, and combinations thereof. For example, the metal filler can include aluminum particles having an aluminum oxide layer on its surface. Inorganic fillers are exemplified by onyx; metal oxides such as aluminum trihydrate, aluminum oxyhydrate, aluminum oxide, beryllium oxide, magnesium oxide, and zinc oxide; nitrides such as aluminum nitride; carbides such as silicon carbide and tungsten carbide, and combinations thereof. Alternatively, inorganic fillers are exemplified by aluminum oxide, zinc oxide, and combinations thereof.

[0137] Alternatively, the (F) filler may comprise a non-reactive silicone resin. For example, the (F) filler may comprise a non-reactive MQ silicone resin. As is known in the art, the M siloxy units are represented by R 0 3SiO 1 / 2 and the Q siloxy unit is SiO 4 / 2 wherein R 0are independently selected substituents. Such non-reactive silicone resins are typically soluble in liquid hydrocarbons such as benzene, toluene, xylene, heptane, or liquid organosilicon compounds such as low viscosity cyclic and linear polydiorganosiloxanes. The molar ratio of M to Q siloxy units in the non-reactive silicone resin can be 0.5 / 1 to 1.5 / 1, alternatively 0.6 / 1 to 0.9 / 1. The non-reactive silicone resin can further comprise 2.0 wt. % or less, alternatively 0.7 wt. % or less, alternatively 0.3 wt. % or less of T units containing silicon-bonded hydroxyl groups or hydrolyzable groups, exemplified by alkoxy, e.g., methoxy and ethoxy, and acetoxy, while still being within the scope of such non-reactive silicone resins. The concentration of hydrolyzable groups present in the non-reactive silicone resin can be determined using Fourier transform infrared (FT-IR) spectroscopy.

[0138] Alternatively or additionally, (F) filler may comprise a non-reactive silicone resin other than the non-reactive MQ silicone resin just described. For example, (F) filler may comprise a T resin, a TD resin, a TDM resin, a TDMQ resin, or any other non-reactive silicone resin. Typically, such non-reactive silicone resins comprise at least 30 mole percent T siloxy and / or Q siloxy units. As is known in the art, D siloxy units are represented by R 0 2SiO 2 / 2 and the T siloxy unit is represented by R 0 SiO 3 / 2 wherein R 0 are independently selected substituents.

[0139] Weight average molecular weight of non-reactive silicone resin, M w M depends, at least in part, on the molecular weight of the silicone resin and the type of substituents (e.g., hydrocarbyl groups) present in the non-reactive silicone resin. wrepresents the weight average molecular weight measured using conventional gel permeation chromatography (GPC) with narrow molecular weight distribution polystyrene (PS) standard calibration when the peak representing the neopentamer is excluded from the measurement. The PS equivalent M of the non-reactive silicone resin w can be 12,000 to 30,000 g / mol, typically 17,000 to 22,000 g / mol. The non-reactive silicone resin can be prepared by any suitable method. This type of silicone resin has been prepared by the hydrolysis method of the corresponding silane or by the silica hydrosol capping method, which are generally known in the art.

[0140] Regardless of the selection of the (F) filler, the (F) filler may be added to form the adhesive untreated, pretreated, or in combination with an optional filler treatment, which when so added may treat the (F) filler in situ in the adhesive.

[0141] The filler treating agent may include a silane such as an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclic polyorganosiloxane, a hydroxyl-functional oligosiloxane such as dimethylsiloxane or methylphenylsiloxane, an organosilicon compound, stearic acid, or a fatty acid. The filler treating agent may include a single filler treating agent or may include a combination of two or more filler treating agents selected from similar or different types of molecules.

[0142] The filler treating agent may include an alkoxysilane, which may be a monoalkoxysilane, a di-alkoxysilane, a tri-alkoxysilane, or a tetraalkoxysilane. Examples of alkoxysilane filler treating agents include hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinations thereof. In certain embodiments, the alkoxysilane may be used in combination with a silazane that catalyzes the reaction of the less reactive alkoxysilane with the surface hydroxyl. Such reactions are typically carried out at temperatures above 100°C, with high shear, and with removal of volatile by-products such as ammonia, methanol, and water.

[0143] Suitable filler treating agents include alkoxysilyl-functional alkylmethylpolysiloxanes or similar materials in which the hydrolyzable groups can include, for example, silazane, acyloxy, or oximo.

[0144] Alkoxy-functional oligosiloxanes can also be used as filler treating agents. Alkoxy-functional oligosiloxanes and methods for their preparation are generally known in the art. Other filler treating agents include mono-end-capped alkoxy-functional polydiorganosiloxanes, i.e., polyorganosiloxanes having an alkoxy functionality at one end.

[0145] Alternatively, filler treating agent can be any of the organosilicon compounds typically used for treating silica filler.The examples of organosilicon compounds include organochlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane and trimethylmonochlorosilane; organosiloxanes such as hydroxyl endblocked dimethylsiloxane oligomers, silicon hydride functional siloxanes, hexamethyldisiloxane and tetramethyldivinyldisiloxane; organosilazanes such as hexamethyldisilazane and hexamethylcyclotrisilazane; and organoalkoxysilanes such as alkylalkoxysilanes with methyl, propyl, n-butyl, i-butyl, n-hexyl, n-octyl, i-octyl, n-decyl, dodecyl, tetradecyl, hexadecyl or octadecyl substituents. The organic reactive alkoxysilane may include amino, methacryloxy, vinyl, glycidoxy, epoxycyclohexyl, isocyanurate, isocyanato, mercapto, sulfide, vinyl-benzyl-amino, benzyl-amino, or phenyl-amino substituents. Alternatively, the filler treating agent may include an organopolysiloxane. The use of such filler treating agents to treat the surface of the (F) filler may utilize multiple hydrogen bonds, either clustered or dispersed, or both, as a method of bonding the organosiloxane to the surface of the (F) filler. The hydrogen-bondable organosiloxane has, on average, at least one silicon-bonded group capable of hydrogen bonding per molecule. The group may be selected from monovalent organic groups with multiple hydroxyl functionalities or monovalent organic groups with at least one amino functional group. Hydrogen bonding may be the primary mode of bonding of the filler treating agent to the (F) filler. The filler treating agent may not be capable of forming covalent bonds with the (F) filler. The hydrogen-bondable filler treating agent may be selected from the group consisting of sugar-siloxane polymers, amino-functional organosiloxanes, and combinations thereof. Alternatively, the hydrogen-bondable filler treating agent may be a saccharide-siloxane polymer.

[0146] Alternatively, the filler treating agent may include alkyl thiols, such as octadecyl mercaptan, and fatty acids, such as oleic acid, stearic acid, titanates, titanate coupling agents, zirconate coupling agents, and combinations thereof. One of ordinary skill in the art would be able to optimize the filler treating agent to aid in the dispersion of the (F) filler without undue experimentation.

[0147] If utilized, the relative amounts of the filler treating agent and (F) filler are selected based on the particular filler utilized, as well as the filler treating agent and their desired effects or properties. Combinations of different fillers and / or filler treating agents may also be utilized.

[0148] The amount of (F) filler utilized, if any, is a function of many variables. In certain embodiments, the adhesive comprises a filler in an amount of 20-70 wt.%, alternatively 30-60 wt.%, based on the total weight of the adhesive.

[0149] In certain embodiments, the adhesive further comprises a (G) catalyst for promoting the reaction between the isocyanate functional group of the urethane prepolymer and atmospheric moisture, so that a reaction occurs between them when the adhesive is exposed to ambient moisture, for example, when dispensed from a can or cylinder. Examples of such (G) catalysts include amine catalysts, metal complexes, or combinations thereof. Amine catalysts can include organic compounds containing at least one tertiary nitrogen atom (e.g., tertiary amines). Examples include amidines or guanidines such as, for example, 4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), triethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N,N-dimethylcyclohexylamine, N-ethyl-morpholine, 2,2'-dimorpholinodiethyl ether ("DMDEE"), 2-methylpropanediamine, methyltriethylenediamine, 2,4,6-tri(dimethylaminomethyl)phenol, N,N',N''-tris(dimethylamino-propyl)sym-hexahydrotriazine, and mixtures thereof. In further embodiments, the amine catalyst comprises bis(2-dimethylamino-ethyl)ether, dimethylcyclohexylamine, N,N-dimethyl-ethanolamine, triethylenediamine, triethylamine, 2,4,6-tri(dimethylaminomethyl)phenol, N,N',N-ethylmorpholine, organometallic catalysts based on tin, zinc and bismuth, such as dibutyltin dilaurate, and / or mixtures thereof.

[0150] In some embodiments, the adhesive comprises a (H) plasticizer. Examples of suitable (H) plasticizers include organic plasticizers such as those comprising carboxylic acid esters (e.g., esters), phthalates (e.g., phthalates), carboxylates (e.g., carboxylates), adipates (e.g., adipates), or combinations thereof. Specific examples of suitable organic plasticizers include bis(2-ethylhexyl) terephthalate, bis(2-ethylhexyl)-1,4-benzenedicarboxylate, 2-ethylhexylmethyl-1,4-benzenedicarboxylate, 1,2 cyclohexanedicarboxylic acid, dinonyl esters (branched and linear), bis(2-propylheptyl) phthalate, diisononyl adipate, and combinations thereof.

[0151] In certain embodiments, the (H) plasticizer has, on average, a compound represented by the formula:

[0152] [ka] [In the formula, R 17 represents a hydrogen atom or a monovalent organic group (e.g., a branched or linear monovalent hydrocarbon group such as an alkyl group having 4 to 15 carbon atoms or 9 to 12 carbon atoms). In these or other embodiments, the plasticizer has an average of at least two groups of the above formula per molecule, each bonded to a carbon atom in a cyclic hydrocarbon. In such cases, the plasticizer has the following general formula:

[0153] [ka] may have:

[0154] In this formula, D is a carbocyclic group having 3 or more carbon atoms, or 3 to 15 carbon atoms, which may be unsaturated, saturated, or aromatic. The subscript E is 1 to 12. Each R 18are each independently a branched or linear monovalent hydrocarbon group such as an alkyl group having 4 to 15 carbon atoms (e.g., an alkyl group such as a methyl group, an ethyl group, or a butyl group). 19 are independently a hydrogen atom or a branched or linear, substituted or unsubstituted monovalent organic group. For example, in some embodiments, at least one R 19 is a moiety that contains an ester functionality.

[0155] In a specific embodiment, the adhesive comprises a polymeric plasticizer. Examples of polymeric plasticizers include alkenyl polymers (e.g., alkenyl polymers obtained by polymerizing vinyl or allylic monomers by various methods); polyalkylene glycol esters (e.g., diethylene glycol dibenzoate, triethylene glycol, dibenzoate pentaerythritol esters, etc.); polyester plasticizers (e.g., polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol); polyesters including polyester polyols each having a molecular weight of 500 or more (e.g., polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.); polystyrenes (e.g., polystyrene, poly-α-methylstyrene, etc.); polybutenes and polybutadienes (e.g., polyisobutylene, butadiene acrylonitrile, etc.); and polychloroprene. In various embodiments, low molecular weight plasticizers and high molecular weight polymeric plasticizers can be present in combination in the adhesive.

[0156] Suitable plasticizers are known in the art and commercially available. Such plasticizers may be present in the adhesive alone or in combination. For example, plasticizers include: phthalates, such as dialkyl phthalates, such as dibutyl phthalate (Eastman® DBP Plasticizer), diheptyl phthalate, diisononyl phthalate, di(2-ethylhexyl) phthalate, or diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate (BASF Palatinol® DPHP), di(2-ethylhexyl) phthalate (Eastman® DOP Plasticizer), dimethyl phthalate (Eastman® DMP Plasticizer); diethyl phthalate (Eastman® DMP Plasticizer); butyl benzyl phthalate, and bis(2-ethylhexyl) terephthalate (Eastman® 425 Plasticizer); dicarboxylates, such as benzyl, C7-C9 linear and branched alkyl esters, 1,2,benzyl dicarboxylic acid (Ferro SANTICIZER™ 261A), 1,2,4-benzenetricarboxylic acid (BASF Palatinol™ TOTM-I), bis(2-ethylhexyl)-1,4-benzenedicarboxylate (Eastman™ 168 Plasticizer); 2-ethylhexylmethyl-1,4-benzenedicarboxylate; branched and linear 1,2 cyclohexanedicarboxylic acid dinonyl esters (BASF Hexamoll™ DINCH); diisononyl adipate; trimellitates, e.g., trioctyl trimellitate (Eastman™ TOTM Plasticizer); triethylene glycol bis(2-ethylhexanoate) (Eastman™ TEG-EH Plasticizer); triacetin (Eastman™ Triacetin);Non-aromatic dibasic acid esters such as dioctyl adipate, bis(2-ethylhexyl) adipate (Eastman™ DOA Plasticizer and Eastman™ DOA Plasticizer, Kosher), di-2-ethylhexyl adipate (BASF Plastomoll™ DOA), dioctyl sebacate, dibutyl sebacate and diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl resinolate; phosphates such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; hydrocarbon oils such as alkyl diphenyls and partially hydrogenated terphenyls; process oils, epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; tris(2-ethylhexyl) esters; fatty acid esters; and combinations thereof. Other suitable plasticizers and commercial sources thereof include BASF Palamoll™ 652 and Eastman 168 Xtreme™ plasticizers.

[0157] The amount of (H) plasticizer present in the adhesive will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials (e.g., other polymeric additives) present in the adhesive, the type of crosslinker used, etc.) and can be readily determined by one of ordinary skill in the art. Generally, if present, the adhesive will include plasticizer in an amount of greater than 0 weight percent to 20 weight percent, or 5 weight percent to 15 weight percent, based on the total weight of the adhesive.

[0158] In certain embodiments, the adhesive further comprises an (I) adhesion promoter. Suitable (I) adhesion promoters may include hydrocarbon oxysilanes such as alkoxysilanes, combinations of alkoxysilanes and hydroxy-functional polyorganosiloxanes, amino-functional silanes, epoxy-functional silanes, mercapto-functional silanes, or combinations thereof. Adhesion promoters are known in the art and may be represented by the formula: R 5 f R 6g Si(OR 7 ) 4-(f+g) [In the formula, each R 5 are independently a monovalent organic group having at least 3 carbon atoms; R 6 contains at least one SiC-bonding substituent having an adhesion-promoting group, such as an amino group, an epoxy group, a mercapto group, or an acrylate group, and each R 7 are independently a monovalent organic radical (e.g., methyl, ethyl, propyl, butyl, etc.), subscript f has a value ranging from 0 to 2, subscript g is either 1 or 2, and the sum of (f+g) is 3 or less. In certain embodiments, the (I) adhesion promoter comprises a partial condensate of the above silanes. In these or other embodiments, the (I) adhesion promoter comprises a combination of an alkoxysilane and a hydroxy-functional polyorganosiloxane.

[0159] In some embodiments, the (I) adhesion promoter comprises an unsaturated or epoxy-functional compound. In such embodiments, the adhesion promoter comprises an unsaturated or epoxy-functional alkoxysilane, such as a silane having the formula (XIII): R 8 h Si(OR 9 ) (4-h) where subscript h is 1, 2, or 3, or subscript h is 1. Each R 8 are independently monovalent organic groups, provided that at least one R 8 R is an unsaturated organic group or an epoxy-functional organic group. 8 The epoxy-functional organic groups are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. 8 The unsaturated organic groups of R are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl, and the like. 9 R is independently a saturated hydrocarbon group having 1 to 4 carbon atoms or 1 to 2 carbon atoms. 9is exemplified by methyl, ethyl, propyl, and butyl.

[0160] Specific examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

[0161] In some embodiments, the (I) adhesion promoter comprises an epoxy-functional siloxane (e.g., any of those described above), such as a reaction product of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane, or a physical blend of a hydroxy-terminated polyorganosiloxane with an epoxy-functional alkoxysilane. The (I) adhesion promoter may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the (I) adhesion promoter is exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane with a reaction product of a hydroxy-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane with a hydroxy-terminated methylvinylsiloxane / dimethylsiloxane copolymer.

[0162] In certain embodiments, (I) the adhesion promoter is H2N(CH2)2Si(OCH3)3, H2N(CH2)2Si(OCH2CH3)3, H2N(CH2)3Si(OCH3)3, H2N(CH2)3Si(OCH2CH3)3, CH3NH(CH2)3Si(OCH3)3, CH3NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)5Si(OCH3)3, CH3NH(CH2)5Si(OCH2CH3)3, H2N(CH2)2NH(CH2)3Si (OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH2CH3)3, C4H9NH( CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(CH2)2SiCH3(OCH3)2, H2N(CH2)2SiCH3(OCH2CH3)2, H2N( CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)5S iCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH and amino-functional silanes such as amino-functional alkoxysilanes exemplified by (CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3), N-(3-(trimethoxysilyl)propyl)ethylenediamine, and the like, and combinations thereof. In these or other embodiments, the (I) adhesion promoter comprises a mercapto-functional alkoxysilane, such as 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.

[0163] An additional example of an adhesion promoter is the reaction product of an epoxyalkylalkoxysilane, such as 3-glycidoxypropyltrimethoxysilane, with an amino-substituted alkoxysilane, such as 3-aminopropyltrimethoxysilane, and optionally with an alkylalkoxysilane, such as methyltrimethoxysilane.

[0164] The amount of (I) adhesion promoter in the adhesive will vary depending on a variety of factors (e.g., the amount and / or type of urethane prepolymer, the type and / or amount of any additional materials present in the adhesive, the cure conditions to which the adhesive is intended to be exposed, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the adhesive will include (I) adhesion promoter in an amount of 0.01 to 10 weight percent, alternatively 0.01 to 5 weight percent, alternatively 0.01 to 2.5 weight percent, based on the total weight of the adhesive.

[0165] In certain embodiments, the adhesive includes a desiccant, such as a physical desiccant (e.g., an adsorbent), a chemical desiccant, etc. In general, the desiccant binds water and low molecular weight alcohols from various sources. For example, the desiccant may bind to by-products of a condensation reaction involving at least one silicone-polyether copolymer, such as water and alcohol. A physical desiccant typically captures and / or adsorbs such water and / or by-products, while a chemical desiccant typically binds water and / or other by-products by chemical means (e.g., via covalent bonds). Examples of desiccants suitable for use in the adhesive include adsorbents, such as those that include inorganic particulates. Such adsorbents typically have a particle size of 10 micrometers or less or 5 micrometers or less and an average pore size sufficient to adsorb water and low molecular weight alcohols (e.g., an average pore size of 10 Å (angstroms) or less, or 5 Å or less, or 3 Å or less). Specific examples of such adsorbents include zeolites (e.g., chabazite, mordenite, and analcime), and molecular sieves including alkali metal aluminosilicates, silica gel, silica-magnesia gel, activated carbon, activated alumina, calcium oxide, and combinations thereof. Examples of commercially available desiccants include the 3 Å (angstrom) molecular sieve sold under the trade name SYLOSIV™ by Grace Davidson and under the trade name PURMOL by Zeochem of Lousville, Kentucky, USA, and the 4 Å molecular sieve sold under the trade name Doucil zeolite 4A by Ineos Silicas of Warrington, UK. Other examples of suitable desiccants include MOLSIV ADSORBENT TYPE 13X, 3A, 4A, and 5A molecular sieves, all of which are commercially available from UOP, Illinois, USA; SILIPORITE NK 30AP and 65xP from Atofina, Philadelphia, Pennsylvania, USA; and molecular sieves commercially available from W.R. Grace. Examples of chemical desiccants include silanes, such as those described above with respect to crosslinkers.For example, alkoxysilanes suitable as desiccants include vinyltrimethoxysilane, vinyltriethoxysilane, and combinations thereof. As will be appreciated by those skilled in the art, a chemical desiccant can be added to the adhesive or to a portion of the adhesive (e.g., if the adhesive is a multi-part composition) to keep the adhesive or a portion thereof free of water. Thus, the desiccant can be added to a portion of the adhesive (e.g., the dry portion) before the adhesive is formed, thereby rendering the portion storable. Alternatively, or in addition, the desiccant can keep the adhesive free of water after formulation (e.g., after the portions of the adhesive are combined / mixed together). The amount of desiccant present in the adhesive will vary depending on a variety of factors (e.g., the amount and / or type of at least one silicone-polyether copolymer, the type and / or amount of any additional materials present in the adhesive, the curing conditions to which the adhesive is intended to be exposed, etc.) and can be readily determined by one skilled in the art. Generally, if present, the adhesive will include a desiccant in an amount of 0.1 to 5 parts by weight, based on the total weight of all components in the adhesive.

[0166] In certain embodiments, the adhesive comprises a rheological additive, such as a rheological modifier and / or a viscosity modifier. Examples of suitable rheological additives include waxes; polyamides, polyamide waxes; hydrogenated castor oil derivatives; metal soaps, such as calcium, aluminum, and / or barium stearate, and derivatives, modifications, and combinations thereof. In certain embodiments, the rheological modifier is selected to facilitate the incorporation of fillers, compounding, degassing, and / or mixing (e.g., during preparation) of the adhesive, as will be well understood by those skilled in the art. Specific examples of rheological additives include those commercially available and known in the art. Examples of such rheological additives include Polyvest, available from Evonik; Disparlon, available from King Industries; Kevlar Fibre Pulp, available from Du Pont; Rheospan, available from Nanocor; Ircogel, available from Lubrizol; Crayvallac™ SLX, available from Palmer Holland, and the like, and combinations thereof.

[0167] The amount of rheological additive present in the adhesive will vary depending on a variety of factors (e.g., amount and / or type of urethane prepolymer, intended use of the adhesive, cure conditions to which the adhesive is intended to be exposed, presence or absence of a vehicle / solvent, etc.) and can be readily determined by one of ordinary skill in the art. Generally, when present, the adhesive will include rheological additive in an amount of greater than 0 to 20 parts by weight, or 1 to 15 parts by weight, or 1 to 5 parts by weight, based on the total weight of all components in the adhesive.

[0168] The adhesive may optionally further comprise an additive component, which may be selected from the group of crosslinkers, chain terminators, wetting agents, surface modifiers, surfactants, waxes, dyes, pigments, colorants, flame retardants, release agents, antioxidants, compatibilizers, UV stabilizers, thixotropic agents, anti-aging agents, lubricants, coupling agents, flame retardants, smoke suppressants, antistatic agents, antimicrobial agents, and combinations thereof.

[0169] One or more of the additives can be present in any suitable weight percentage (wt %) of the adhesive, such as, for example, 0.1 wt % to 15 wt %, 0.5 wt % to 5 wt %, or 0.1 wt % or less, 1 wt %, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt % or more of the adhesive. Those of ordinary skill in the art can readily determine suitable amounts of additives depending, for example, on the type of additive and the desired result.

[0170] The adhesives can be prepared by combining the components in any order of addition, optionally under shear. The adhesives can be prepared in situ in the end-use application, i.e., the components can be combined during the end-use application of the adhesive, or can be formed and subsequently utilized. If necessary, at least one condition can be selectively changed during the formation of the adhesive, such as temperature, humidity, pressure, etc. The adhesives can be one-component, two-component, or multi-component. Further aspects of the methods of preparing and using the adhesives are disclosed in International Application No. PCT / US2020 / 012182, which is incorporated herein by reference. EXAMPLES

[0171] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way.

[0172] Certain specific ingredients utilized in the examples are set forth in Table 1 below.

[0173] [Table 1]

[0174] General procedure for the preparation of active Raney Ni catalysts Raney Ni™ 50 wt. % in water was purchased and washed several times with deionized water in a plastic funnel. Special care was taken to ensure the catalyst was always submerged in water (as Raney Ni™ is highly pyrophoric). The water was then exchanged for isopropanol (IPA) by slowly siphoning the water via vacuum while adding IPA. The catalyst was washed several more times with IPA and transferred to a glass bottle as a suspension of Raney Ni active catalyst.

[0175] General procedure for one-pot hydroformylation / hydrogenation reactions

[0176] [ka] General reaction scheme for the one-pot hydroformylation / hydrogenation reaction In a nitrogen filled glove box, a stock solution of catalyst was prepared with Rh(acac)(CO)2 (8.2 mg), ligand (53 mg), and toluene (130 g) weighed into a 200 mL glass bottle. From this stock solution, the desired amount was transferred into an airtight syringe equipped with a metal valve and subsequently removed from the glove box. In a ventilated fume hood, the alkenyl functional siloxane (100-1000 g) was transferred into a Parr reactor. The reactor was sealed and mounted in a holder. The reactor was pressurized to 100 psi with nitrogen and carefully released three times through the valve connected to the headspace. The reactor was then pressure tested by pressurizing to 200 psi with nitrogen. After releasing the pressure, the stock solution was added to the reactor via the septa port. The reactor was pressurized to 100 psi with syngas and carefully released three times. It was then pressurized to 100 psi, and then stirring (800 rpm) and heating (70°C) were started. Typical reaction times were 4-6 hours. To monitor the reaction, the reactor temperature was cooled to below 60°C, the pressure was released, and samples were carefully withdrawn through a dip tube and 1 The reaction was analyzed by H NMR. After the reaction was complete, the reactor was cooled to ambient temperature and depressurized. The reactor was then pressurized with N2 and depressurized three times before removing the seal and lowering the reactor.

[0177] A certain amount of Raney Ni active catalyst (10-15 wt%) was scooped from the glass bottle and carefully loaded into the reaction vessel with a minimal amount of IPA. The reactor was quickly reassembled and purged with N2 three times. The reactor was then pressure tested by pressurizing to 400 psi of N2. The reactor was pressurized with hydrogen and carefully released three times. It was then pressurized to 200 psi with hydrogen and stirring (800 rpm) and heating (80°C) were started. To monitor the reaction, the reactor temperature was cooled to below 60°C, the pressure was released and a sample was carefully withdrawn via a dip tube and cooled. 1 The reaction was analyzed by H NMR. After the reaction was completed, the reactor was cooled to ambient temperature and depressurized. The reactor was then purged with N2 three times, after which the seal was removed and the reactor was lowered. The slurry was transferred to an Erlenmeyer flask with a minimum amount of toluene. The slurry was then filtered by vacuum filtration, followed by stripping the solvent using a rotary evaporator (20 Torr, 50°C) to obtain the crude product. Finally, the crude product was pressure filtered under N2 using a 0.2 micron PTFE filter to obtain the carbinol-functional siloxane in the form of an optically clear fluid.

[0178] Procedure for the ethoxylation of silicon-bonded carbinol groups:

[0179] [ka] Specific reaction scheme for the ethoxylation of polyether-functional siloxanes 75 g of the carbinol functional siloxane and 0.075 g (1000 ppm) were combined in a flask with stirring to give a solution. This solution was transferred via syringe to a batch reactor under nitrogen and heated to 60° C. Ethylene oxide (44.1 g, 1.0 mol) was added to the batch reactor at 60° C. with stirring at a rate of 1 mL / min. At the end of the addition over approximately 1 hour, stirring at 60° C. was continued for an additional 3 hours. Any remaining ethylene oxide was purged with nitrogen, the resulting mixture was cooled, and the recovered product (106.4 g) was 1 The recovered product was analyzed by H NMR. The NMR test results confirmed that the recovered product was a polyether-functional siloxane formed by the alkoxylation of a carbinol-functional siloxane.

[0180] Table 2 below shows the Mn, Mw, and PDI of the carbinol-functional siloxanes and polyether-functional siloxanes measured by gel permeation chromatography (GPC). Specifically, the carbinol-functional siloxanes and polyether-functional siloxanes were dissolved at a concentration of 2.0 mg / mL in tetrahydrofuran (THF) stabilized with 250 ppm butylated hydroxyltoluene (BHT). The samples were shaken to dissolve the solids for GPC analysis. GPC / SEC analysis was performed using an Agilent 1260 Infinity system equipped with a refractive index detector and a column with a linear MW operating range up to 30,000 g / mol. Samples (100 μL) were eluted through one PL-gel 3 μm×50×7.5 mm guard column followed by two PL-gel 3 μm×300×7.5 mm mixed-E columns maintained at 35° C. with BHT-stabilized THF at a flow rate of 1.00 mL / min. Total run time was 23.00 min. Agilent EasiVial PS-L polystyrene standards were diluted to 1.5 mL with BHT-stabilized THF and analyzed under the same run conditions as above to generate a 12-point MW calibration curve. This third-order calibration curve was applied to the sample results to determine MW characteristics.

[0181] [Table 2]

[0182] As shown in Table 2, both the molecular weight and PDI are increased by ethoxylation of the carbinol-functional siloxane. Furthermore, the MW distribution of the polyether-functional siloxane was monomodal, whereas the MW distribution of the conventional polyether-functional siloxane prepared by hydrosilylation is bimodal. Figure 1 shows the RI signal as a function of elution time for the polyether-functional siloxane and the comparative polyether-functional siloxane composition.

[0183] Example 1 and Comparative Example 1 In Example 1 and Comparative Example 1, isocyanate-functional prepolymers were prepared using the polyether-functional siloxane and comparative polyether-functional siloxane compositions prepared above. The polyether-functional siloxane was identical to the comparative polyether-functional siloxane composition, except for its synthesis method and associated impurities. Specifically, as described above, the polyether-functional siloxane was synthesized by hydroformylation, hydrogenation (or reduction), and alkoxylation. In contrast, the comparative polyether-functional siloxane composition was prepared by hydrosilylation between a siloxane having a terminal dimethylhydrogensilyl group and a polyether compound having an allyl functional group at one end in the presence of a platinum catalyst. As a result, the comparative polyether-functional siloxane composition contains a residual amount of polyether compound that was not hydrosilylated to the polyether-functional siloxane of the polyether-functional siloxane composition, and the polyether compound cannot be easily removed therefrom. Table 3 below shows the amount of each component utilized to prepare the isocyanate-functional prepolymers of Example 1 and Comparative Example 1. Each of the isocyanate-functional prepolymers contained an isocyanate functional group at each end based on the specific components utilized in Example 1 and Comparative Example 1.

[0184] To prepare the isocyanate-functional prepolymers, polyols 1 and 2 and the polyether-functional siloxane and comparative polyether-functional siloxane compositions were dried overnight with a nitrogen purge and used only if the moisture content was measured to be less than 300 ppm. All other ingredients were stored and used in a glove box. The reaction vessels (glass vials) were dried in an oven at 110° C. for at least 24 hours.

[0185] In Example 1 and Comparative Example 1, the isocyanate-functional prepolymers were prepared in 30 mL glass vials that had been pre-dried in a glove box. All ingredients except the catalyst were added to the vials and then mixed for 60 seconds at 3000 rpm using a FlackTek Inc. Speed ​​Mixer (Model DCV DAC 150 FVZ-K). The catalyst was then added to each vial and mixed for 60 seconds at 3000 rpm using the FlackTek. The vials were removed from the glove box and then placed in a Despatch Class A oven at 80° C. for 4 hours to complete the preparation of each isocyanate-functional prepolymer.

[0186] [Table 3]

[0187] The isocyanate-functional prepolymers prepared in Example 1 and Comparative Example 1 were analyzed by GPC. These isocyanate-functional prepolymers were first derivatized. Specifically, about 0.15 g of each isocyanate-functional prepolymer was weighed into a glass vial and dissolved in 10 mL of a mixture of methanol (MeOH) and tetrahydrofuran (THF) (THF:MeOH=1:1 (v / v)) to obtain a solution. The solution was shaken until each isocyanate-functional prepolymer was dissolved. Then, 5 μL of dibutyltin dilaurate catalyst solution (100 mg dibutyltin dilaurate in 1 mL THF) was added. The solution was reacted with methanol overnight or until no isocyanate was detected by FT-IR. After no isocyanate was detected, the solution was diluted with THF to a concentration of about 0.2 wt % by adding 0.4 g of each solution to 12 g THF. The solution was filtered through a 0.45 μm PTFE syringe filter before injection. The molecular weight and molecular weight distribution were determined using GPC.

[0188] GPC was performed with a Waters 2695LC pump and autosampler. The flow rate was set at 1 mL / min and the injection volume was set at 50 uL. GPC separation was performed on two Agilent PLgel mixed-C columns (7.5 mm ID x 300 mm length) held at 35°C. The detector was a Shodex RI 201 refractive index detector held at 35°C.

[0189] Agilent GPC software Cirrus version 3.3 was used for data collection and data reduction. A total of 16 PS linear narrow molecular weight standards from Agilent with Mp values ​​ranging from 2,750 to 0.58 kg / mol were used for molecular weight calibration. A third order polynomial was used for calibration curve fitting. Therefore, all references to molecular weight averages, distributions and molecular weights are in PS terms. Figure 2 shows the RI signal as a function of elution time for the isocyanate-functional prepolymers of Example 1 and Comparative Example 1.

[0190] Crosshatch adhesion test of Example 1 and Comparative Example 1 Preparation of prepolymer coatings for crosshatch adhesion testing Aluminum and glass substrates were wiped with isopropanol (IPA) using a cotton swab and air dried for 10 minutes. Each isocyanate-functional prepolymer was then coated onto the substrate using a drawdown bar to produce a 6 mil (150 micron) wet coating. The coatings were allowed to cure at room temperature in a humidity controlled room (50% RH) for approximately 2 weeks.

[0191] Crosshatch adhesion test Crosshatch adhesion is used to evaluate the adhesive strength of a coating to a substrate. In the crosshatch adhesion test, a crosshatch scribe is used to make parallel linear cuts through the coating. A similar set of linear cuts were made perpendicular to the original cuts to obtain a checkerboard pattern. Tape (3M#810) was applied to the scribed surface and rubbed with a finger to apply the appropriate pressure. The free end of the tape was then pulled smoothly at a 135° angle to remove the tape from the surface of each coating. The coatings were then visually evaluated for adhesion and the adhesive strength was measured / ranked according to ASTM D3359. For coatings with poor adhesion to the substrate, most of the squares in the checkerboard pattern are removed by the ASTM tape. In contrast, for coatings with excellent adhesion, none (or very few) of the scribed squares are removed. Adhesion was ranked from 0 to 5. The adhesive strength was directly proportional to the ranking number, as shown in Table 4 below.

[0192] [Table 4]

[0193] Table 5 below shows the crosshatch adhesion test results for the cured products of the isocyanate-functional prepolymers of Example 1 and Comparative Example 1, respectively.

[0194] [Table 5]

[0195] It is to be understood that the scope of the appended claims is not limited to the language in the "Description of Embodiments" section, nor to the specific compounds, compositions, or methods described therein, which may vary among specific embodiments falling within the scope of the appended claims.

Claims

1. (A) Carbinol-functionalized siloxane, (B) A composition comprising a polyisocyanate, The carbinol-functionalized siloxane (A) is not prepared by a hydrosilylation reaction, and the composition contains less than 5 moles of formula (C) R-O ａ - (C ｂ H ２ｂ O) ｃ -R １ The compound (wherein R is an ethylenically unsaturated group, R １ A composition comprising (where is H or a hydrocarbyl group, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each part indicated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not both 0 at the same time).

2. (i) The (A) carbinol-functional siloxane contains two or more carbinol functional groups, and (ii) the carbinol functional group has the general formula -D-O ａ -(C ｂ H ２ｂ O) ｃ -H (where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each part represented by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not both 0 at the same time), or (iii) both (i) and (ii), the composition according to claim 1.

3. The carbinol-functionalized siloxane described above (A) is given by the following general formula: 【Chemistry 1】 (In the formula, each R ２ R is an independently selected hydrocarbyl group or carbinol functional group, wherein at least one R ２ (where n is a carbinol functional group, and the subscript n is between 0 and 100) or the following general formula: 【Chemistry 2】 (In the formula, each R ２ The composition according to claim 1, wherein is an independently selected hydrocarbyl group, the subscript n is 0 to 100, and each of the subscripts m is independently 1 to 100.

4. The carbinol-functionalized siloxane described above (A) is i) Under conditions that catalyze the hydroformylation reaction, (I) A gas containing hydrogen and carbon monoxide, (II) Alkenyl-functionalized siloxanes, (III) Rhodium / bisphospite ligand complex catalyst and A process involving the combination of starting materials including, Optionally, ii) recover the aldehyde-functionalized siloxane, iii) Combining a starting material comprising the aldehyde-functionalized siloxane, hydrogen, and a hydrogenation catalyst under conditions that catalyze the hydrogenation reaction, thereby forming a hydrogenation reaction product comprising the carbinol-functionalized siloxane, Optionally, iv) recover the carbinol-functionalized siloxane, Optionally, v) combining a starting material comprising the carbinol-functionalized siloxane, alkylene oxide, and an alkoxylation catalyst under conditions that catalyze the alkoxylation reaction, thereby forming a hydrogenation product comprising the carbinol-functionalized siloxane in the form of a polyether-functionalized siloxane, The composition according to claim 1, formed by a process comprising optionally, vi) recovering the carbinol-functionalized siloxane in the form of a polyether-functionalized siloxane.

5. (D) Polyol and The composition according to claim 1, further comprising optionally (E) a catalyst.

6. A urethane prepolymer comprising the reaction product of the composition according to any one of claims 1 to 5.

7. The urethane prepolymer according to claim 6, wherein the composition contains in component (B) an isocyanate functional group in a stoichiometric excess relative to the total amount of isocyanate reactive groups present in the composition, such that the urethane prepolymer contains at least two isocyanate functional groups.

8. A cured product formed from the composition according to any one of claims 1 to 5 or the urethane prepolymer according to claim 6.

9. A method for preparing the composition according to any one of claims 1 to 5, wherein the method is (A) a carbinol-functionalized siloxane and (B) a polyisocyanate, wherein the carbinol-functionalized siloxane (A) is not prepared by a hydrosilylation reaction, and the composition contains less than 5 moles of (C) formula R-O ａ - (C ｂ H ２ｂ O) ｃ -R １ The compound (wherein R is an ethylenically unsaturated group, R １ A method comprising (where is H or a hydrocarbyl group, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each part indicated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not both 0 at the same time).

10. i) An aldehyde-functionalized siloxane is subjected to conditions that catalyze the hydroformylation reaction. (I) A gas containing hydrogen and carbon monoxide, (II) Alkenyl-functionalized siloxanes, (III) Forming an aldehyde-functionalized siloxane by a process comprising combining a rhodium / bisphospite ligand complex catalyst with starting materials, Optionally, ii) recover the aldehyde-functionalized siloxane, iii) Combining a starting material comprising the aldehyde-functionalized siloxane, hydrogen, and a hydrogenation catalyst under conditions that catalyze the hydrogenation reaction, thereby forming a hydrogenation reaction product comprising the carbinol-functionalized siloxane, Optionally, iv) recover the carbinol-functionalized siloxane, Optionally, v) combining a starting material comprising the carbinol-functionalized siloxane, alkylene oxide, and an alkoxylation catalyst under conditions that catalyze the alkoxylation reaction, thereby forming a hydrogenation product comprising the carbinol-functionalized siloxane in the form of a polyether-functionalized siloxane, The method according to claim 9, further comprising, optionally, vi) preparing the carbinol-functionalized siloxane (A) by a process comprising recovering the carbinol-functionalized siloxane in the form of a polyether-functionalized siloxane.

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